EP1380633B1 - Utilisation de liquides huileux contre l'oxydation des huiles combustibles - Google Patents
Utilisation de liquides huileux contre l'oxydation des huiles combustibles Download PDFInfo
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- EP1380633B1 EP1380633B1 EP03013092.6A EP03013092A EP1380633B1 EP 1380633 B1 EP1380633 B1 EP 1380633B1 EP 03013092 A EP03013092 A EP 03013092A EP 1380633 B1 EP1380633 B1 EP 1380633B1
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- alkylphenol
- fatty acid
- fatty acids
- oils
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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
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- 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
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1835—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
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- 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
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- 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
- C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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- 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
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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- 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
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/013—Iodine value
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/067—Unsaturated Compounds
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
Definitions
- the present invention relates to oils having improved oxidation stability containing fatty acid esters and alkylphenol resins,
- Oils obtained from animal or vegetable material are principally fabric invertebrates comprising triglycerides of monocarboxylic acids, e.g. As acids having 10 to 25 carbon atoms, and the formula in which R is an aliphatic radical of 10 to 25 carbon atoms, which may be saturated or unsaturated.
- oils contain glycerides of a number of acids, the number and variety of which varies with the source of the oil, and they may additionally
- oils Contain phosphoglycerides. Such oils can be obtained by methods known in the art.
- fatty acid alkyl esters are also used as additives for, for example, mineral oils and mineral oil distillates.
- fuel oils with a sulfur content reduced to less than 500 ppm have such poor friction and wear-reducing properties that so-called lubricity additives must be added to them.
- lubricity additives are based inter alia on esters of unsaturated fatty acids with lower alcohols (biodiesel).
- the oily fluids used as fuel oils and additives are mainly based on oils from natural sources such as oilseed rape, sunflowers, soya and similar oilseeds. These have a high content of unsaturated fatty acids of more than 50%, and preferably of more than 80%, which gives them acceptable rheological properties, especially in the cold.
- EP-A-0635558 the use of biodiesel based on C 1 -C 5 -alkyl esters of saturated and unsaturated, straight-chain C 12 -C 22 fatty acids as lubricity improvers for gas oils with low sulfur and aromatic content.
- EP-A-0935645 discloses the use of C 1 -C 30 alkylphenol resins as lubricity additives for low sulfur diesel.
- the examples used are C 18 and C 24 alkylphenol resins.
- WO-99/61562 discloses blends of alkylphenol resins, nitrogen containing compounds and ethylene copolymers as refrigerants and lubricity additives for low sulfur diesel.
- DE-A-10111857 discloses esters of predominantly saturated unbranched monofatty acids with mixtures of C 1 -C 4 monoalcohols with methylated mono- and / or dihydroxybenzenes as an additive to sulfur-free mineral diesel fuel.
- the hydroxybenzenes improve, inter alia, the oxidation stability of the additives.
- the oily liquids based on esters of unsaturated fatty acids which are preferred because of their rheological properties over the esters based on saturated fatty acids, can, on prolonged storage, especially at elevated temperature, harden to only partially oil-soluble products. This can lead to the formation of viscous precipitates and deposits in the storage container as well as in the additized fuel oil. Even in the engine, this can lead to deposits, in particular at the valves and injection nozzles.
- the object of the present invention was therefore to find fuel oils and additives based on unsaturated vegetable and animal oils, which have an improved oxidation stability compared with the prior art.
- esters of unsaturated fatty acids with alkylphenol-aldehyde resins have a significantly improved oxidation stability.
- oily liquids defined above are also referred to below as additives.
- Preferred fatty acids which are part of the esters A) are those having 10 to 26 C atoms, in particular 12 to 22 C atoms.
- the alkyl radicals or alkenyl radicals of the fatty acids consist essentially of carbon and hydrogen. However, they may carry other substituents such as hydroxy, halogen, amino or nitro groups, provided they do not affect the predominantly hydrocarbon character.
- the fatty acids preferably contain at least one double bond. They may contain multiple double bonds, for example 2 or 3 double bonds, and be of natural or synthetic origin. In the case of polyunsaturated carboxylic acids, their double bonds may be isolated or else conjugated. Preference is given to mixtures of two or more unsaturated fatty acids having 10 to 26 carbon atoms.
- fatty acids or fatty acid mixtures contain one or more double bonds.
- the iodine numbers of the Fatty acids or fatty acid mixtures according to the invention are preferably above 50 g J / 100 g, more preferably between 100 and 190 g J / 100 g, in particular between 110 and 180 g J / 100 g and especially between 120 and 180 g I / 100 g fatty acid or fatty acid mixture.
- Suitable unsaturated fatty acids are, for example, oil, eruca, palmitoleic, myristoleic, linoleic, linolenic, elaeosterolic, arachidonic and / or ricinoleic acid.
- dicarboxylic acids such as dimer fatty acids and alkyl- and alkenylsuccinic acids with C 8 -C 50 -alk (en) yl radicals, preferably with C 8 -C 40 -, in particular with C 12 -C 22 -alk (s) ylresten.
- the alkyl radicals can be linear or branched (oligomerized alkenes, polyisobutylene) and saturated or unsaturated. Preference is given to fractions of up to 10% by weight, in particular less than 5% by weight, based on the constituent A).
- the fatty acid mixtures may contain minor amounts, i. up to 20% by weight, preferably less than 10%, in particular less than 5% and especially less than 2% of saturated fatty acids such as, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearin, Contain isostearin, arachin and behenic acid.
- saturated fatty acids such as, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearin, Contain isostearin, arachin and behenic acid.
- the fatty acids can furthermore contain 1-40% by weight, especially 1-25% by weight, in particular 1-5% by weight of resin acids.
- Suitable alcohols contain 1 to 5 carbon atoms. Particularly suitable alcohols are methanol and ethanol, in particular methanol.
- the esters can be prepared from alcohols and fatty acids in a known manner by esterification.
- the transesterification of naturally occurring fats and oils with lower alcohols and in particular with methanol, being by-produced Glycerin is formed.
- alkylphenol-aldehyde resins (B) are known in principle and, for example, in Rompp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351ff , described.
- the alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They may be linear or preferably branched, wherein the branch may contain secondary as well as tertiary structural elements.
- alkylphenol-aldehyde resin can also be up to 20 mol% of phenol units and / or alkylphenols with short alkyl chains such.
- alkylphenol-aldehyde resin the same or different alkylphenols may be used.
- the aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4, carbon atoms and may carry further functional groups. It is preferably an aliphatic aldehyde, more preferably it is formaldehyde.
- the molecular weight of the alkylphenol-aldehyde resins is preferably 350 to 10,000, in particular 400 to 5000, g / mol. This preferably corresponds to a condensation degree n of from 3 to 40, in particular from 4 to 20.
- the prerequisite here is that the resins are oil-soluble.
- these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula wherein R A is C 6 -C 24 alkyl or alkenyl and n is a number from 2 to 50.
- the preparation of the alkylphenol-aldehyde resins is carried out in a known manner by basic catalysis, resulting in resol-type condensation products, or by acid catalysis to form novolac-type condensation products.
- the condensates obtained according to both types are suitable for the compositions according to the invention.
- the condensation is in the presence of acidic catalysts.
- an alkylphenol having 6-24, preferably 8-22, in particular 9-18, carbon atoms per alkyl group, or mixtures thereof, and at least one aldehyde are reacted with each other, wherein about 0.5 mol per mol of alkylphenol compound. 2 mol, preferably 0.7 to 1.3 mol and in particular equimolar amounts of aldehyde are used.
- Suitable alkylphenols are in particular n- and iso-hexylphenol, n- and isoctylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyols (isobutenyl) phenol -C 24th
- the alkylphenols are preferably para-substituted.
- the alkylphenols may carry one or more alkyl radicals. Preferably, they are substituted at most 5 mol%, in particular at most 20 mol% and especially at most 40 mol% with more than one alkyl group. Preferably carry at most 40 mol%, in particular
- the alkylphenols ortho to the hydroxyl group are not substituted with tertiary alkyl groups.
- the aldehyde can be a mono- or dialdehyde and carry other functional groups such as -COOH.
- Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde, glutaric dialdehyde and glyoxylic acid, with formaldehyde being preferred.
- the formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution.
- Corresponding amounts of trioxane can also be used.
- alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali metal hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids.
- alkaline catalysts for example alkali metal hydroxides or alkylamines
- acidic catalysts for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids.
- the condensation is preferably carried out solvent-free at 90 to 200 ° C, preferably at 100 to 160 ° C.
- the reaction takes place in the presence of an organic solvent which forms an azeotrope with water, for example toluene, xylene, higher aromatics or mixtures thereof.
- the reaction mixture is heated to a temperature of 90 to 200 ° C, preferably 100 to 160 ° C, wherein the resulting reaction water is removed during the reaction by azeotropic distillation. Solvents that do not release protons under condensation conditions may remain in the products after the condensation reaction.
- the resins can be used directly or after neutralization of the catalyst, optionally after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, eg gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types.
- aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures eg gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISO
- the proportions by weight of constituents A) and B) in the additives according to the invention can vary within wide limits, depending on the application. They lay preferably between 10 and 99.999% by weight of A), in particular between 20 and 99.995% by weight of A).
- the proportion of components B) is 0.005 to 20 wt .-%.
- Paraffin dispersants are additives which reduce the size of the precipitated wax crystals as the oil cools and, moreover, cause the paraffin particles not to settle but to remain colloidally dispersed with significantly reduced sedimentation effort.
- paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds having ionic or polar groups, for example amine salts, imides and / or amides.
- Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 8 to 36 carbon atoms, in particular dicoco fatty amine, ditallow fatty amine and distearylamine.
- Paraffin dispersants which have been 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 have proven particularly suitable (cf. US 4 211 534 ).
- paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1) and after
- paraffin dispersants are prepared by reacting compounds containing an acyl group with an amine.
- paraffin dispersants can be added to the additives according to the invention or added separately to the middle distillate to be added.
- the amount ratio between paraffin dispersants and the additives according to the invention is between 5: 1 and 1: 5 and preferably between 3: 1 and 1: 3.
- the additives according to the invention can also be used together with one or more oil-soluble co-additives which in themselves improve the lubricity and / or the cold flow properties of crude oils, lubricating oils or fuel oils.
- oil-soluble co-additives are vinyl acetate-containing copolymers or terpolymers of ethylene, comb polymers and oil-soluble amphiphiles.
- the additives according to the invention are mixed with ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, ethylene / vinyl acetate / vinyl neononanoate terpolymers and / or ethylene / vinyl acetate / vinyl neodecanoate terpolymers to simultaneously improve flowability and lubricity of mineral oils or mineral oil distillates.
- the terpolymers of vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, 10 to 35% by weight of vinyl acetate and 1 to 25% by weight of the particular long-chain vinyl ester.
- Other preferred copolymers contain in addition to ethylene and 10 to 35 wt .-% vinyl esters or 0.5 to 20 wt .-% of olefin having 3 to 10 carbon atoms such.
- the additives according to the invention are used together with comb polymers.
- This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone.
- they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms.
- at least 20%, preferably at least 30% of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff ).
- Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1 ), Copolymers of a C 6 -C 24 - ⁇ -olefin and a NC 6 -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.
- the mixing ratio (in parts by weight) of the additives according to the invention with ethylene copolymers or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
- the oily liquids of the invention are particularly suitable for use as fuel oil in diesel engines.
- oils are added to oils as additives in amounts of 0.02 to 10% by weight. They may be used as such or dissolved in solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, diesel, kerosene or commercial solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types, as well as polar solvents such as alcohols, glycols and esters.
- solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, diesel, kerosene or commercial solvent mixtures such as Solvent Naphtha,
- the oily liquids of the invention can be stored at elevated temperature for a long time without aging effects, without causing aging phenomena such as resinification and the formation of insoluble structures or deposits in storage containers and / or engine parts. In addition, they improve the oxidation stability of the oils additized with them. This is particularly advantageous for oils containing larger amounts of cracking oils.
- a further advantage of the oily liquids according to the invention is their crystallization temperature, which is lower than the fatty acid esters used according to the prior art as lubricity additives. So you can also with low temperatures of, for example, 0 ° C to -20 ° C and sometimes lower are used without problems.
- the oily liquids according to the invention are particularly suitable as additives for use in middle distillates.
- 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 oils may also contain or consist of alcohols such as methanol and / or ethanol.
- the additives of the present invention are used in middle distillates containing less than 350 ppm sulfur, more preferably less than 200 ppm sulfur, and in special cases less than 50 ppm and less than 10 ppm sulfur, respectively.
- 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 same are the additives of the invention for use in synthetic fuels with also low lubricity, as z. B. in the Fischer-Tropsch process, suitable.
- the lubricity-enhanced oils have a wear scar diameter measured by the HFRR test of preferably less than 460 ⁇ m, especially less than 450 ⁇ m.
- the oily liquids according to the invention can also be used as components in lubricating oils.
- the oily liquids may be used alone or together with other additives such as pour point depressants, corrosion inhibitors, antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and cloud point depressant additives. Furthermore, they are successfully used together with additive packages containing, among others, known ashless dispersing additives, detergents, defoamers, antioxidants, dehazers, demulsifiers and corrosion inhibitors.
- Iodine numbers are determined by Kaufmann. For this purpose, the sample is mixed with a defined amount of a methanolic bromine solution, wherein an equivalent amount of bromine is added to the content of double bonds. The excess of bromine is back titrated with sodium thiosulfate.
- the mixture After conditioning, the mixture is allowed to cool for one hour at room temperature. Subsequently, 500 ml of diesel fuel (test oil 1) are added and thoroughly mixed. After two hours of use, the mixture is visually assessed for any precipitation, turbidity, insoluble matter, etc., giving evidence of oxidative changes (visual assessment). It is then filtered through a 0.8 micron filter at a pressure difference of 800 mbar. The total amount must be filterable within 2 minutes, otherwise the volume filtered after 2 minutes is noted.
- test oil 1 diesel fuel
- the lubricating effect of the additives was tested by means of an HFRR instrument from PCS Instruments on additized oils at 60 ° C.
- the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 2, p. 217, 1986 , The results are given as coefficient of friction and Wear Scar (WS 1.4).
- a low Wear Scar and a low friction coefficient (Friction) show a good lubricating effect. Wear scar values of less than 460 microns are considered indicative of a sufficient lubricating effect, but in practice, values of less than 400 microns are sought.
- the dosing rates in Table 6 are based on the amount of dosed active ingredient.
- Test oil 1 Test oil 2 distillation IBP [° C] 171 164 20% [° C] 218 214 90% [° C] 323 342 FBP [° C] 352 367 Cloud Point [° C] -8.2 -7.7 CFPP [° C] -12 -13 Density @ 15 ° C [g / cm 3 ] .8262 0.8293 Sulfur [ppm] 15 195 Characterization of the polar nitrogen-containing compounds used C1 Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine, 60% in Solvent Naphtha (prepared according to EP-A-0413279 ) C2 Reaction product of a terpolymer of a C14 / 16- ⁇ -olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% in Solvent Naphtha (prepared according to EP-A-
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Claims (10)
- Utilisation de liquides huileux, contenantA) au moins un ester d'acides gras, dont les longueurs de chaîne carbonée se situent entre 8 et 30 atomes de carbone, et d'un C1-C5-alcool monovalent, au moins 50% des radicaux d'acides gras contenant au moins une double liaison, etB) 0,005 à 20% en poids d'au moins une résine d'alkylphénolaldéhyde, pouvant être obtenue par la condensation de(i) au moins un alkylphénol présentant au moins un radical C6-C24-alkyle ou C6-C24-alcényle et(ii) au moins un aldéhyde ou une cétone,
le degré de condensation étant situé entre 2 et 50 unités d'alkylphénol, dans des huiles combustibles présentant une teneur en soufre d'au maximum 0,035% en poids, en une quantité de 0,02 à 10% en poids, par rapport à l'huile combustible, pour améliorer la stabilité à l'oxydation des huiles combustibles. - Utilisation selon la revendication 1, dans laquelle l'indice d'iode du constituant A) est supérieur à 50 g d'I/100 g d'ester.
- Utilisation selon l'une ou plusieurs des revendications 1 à 2, dans laquelle les acides gras faisant partie du composant A) contiennent 10 à 26 atomes de carbone.
- Utilisation selon l'une ou plusieurs des revendications 1 à 3, dans laquelle les esters d'acides gras A) contiennent au moins 75% en poids d'acides gras présentant une ou plusieurs doubles liaisons.
- Utilisation selon l'une ou plusieurs des revendications 1 à 4, dans laquelle les mélanges d'acides gras contiennent un ou plusieurs acides dicarboxyliques.
- Utilisation selon l'une ou plusieurs des revendications 1 à 5, dans laquelle les alcools dont le constituant A) est dérivé sont le méthanol ou l'éthanol.
- Utilisation selon l'une ou plusieurs des revendications 1 à 6, dans laquelle le constituant A) est dérivé de mélanges d'acides gras qui contiennent jusqu'à 20% en poids d'acides gras saturés.
- Utilisation selon l'une ou plusieurs des revendications 1 à 7, qui contient en outre au moins un dispersant des paraffines contenant de l'azote.
- Utilisation selon l'une ou plusieurs des revendications 1 à 8, qui contient en outre au moins un copolymère d'éthylène.
- Utilisation selon l'une ou plusieurs des revendications 1 à 9, qui contient en outre au moins un polymère en peigne.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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DE10230771 | 2002-07-09 | ||
DE10230771 | 2002-07-09 | ||
DE10252972A DE10252972A1 (de) | 2002-11-14 | 2002-11-14 | Oxidationsstabilisierte ölige Flüssigkeiten auf Basis pflanzlicher oder tierischer Öle |
DE10252972 | 2002-11-14 |
Publications (2)
Publication Number | Publication Date |
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EP1380633A1 EP1380633A1 (fr) | 2004-01-14 |
EP1380633B1 true EP1380633B1 (fr) | 2014-03-26 |
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EP03013092.6A Expired - Fee Related EP1380633B1 (fr) | 2002-07-09 | 2003-06-11 | Utilisation de liquides huileux contre l'oxydation des huiles combustibles |
Country Status (5)
Country | Link |
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US (2) | US20040006912A1 (fr) |
EP (1) | EP1380633B1 (fr) |
JP (1) | JP4754773B2 (fr) |
CA (1) | CA2431748C (fr) |
ES (1) | ES2464840T3 (fr) |
Families Citing this family (9)
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DE10357878C5 (de) | 2003-12-11 | 2013-07-25 | Clariant Produkte (Deutschland) Gmbh | Brennstofföle aus Mitteldestillaten und Ölen pflanzlichen oder tierischen Ursprungs mit verbesserten Kälteeigenschaften |
DE102005045134B4 (de) | 2005-09-22 | 2010-12-30 | Clariant Produkte (Deutschland) Gmbh | Alkylphenol-Aldehydharze, diese enthaltende Zusammensetzungen zu Verbesserung der Kältefließfähigkeit und Schmierfähigkeit von Brennstoffölen sowie deren Verwendung |
US7897824B2 (en) * | 2006-08-16 | 2011-03-01 | Energy & Environmental Research Center Foundation | Optimal energy pathway to renewable domestic and other fuels |
US7655055B2 (en) * | 2006-09-21 | 2010-02-02 | Southwest Research Institute | Biofuel |
EP2036964A1 (fr) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Epaissisant pour fluides de forage à base d'huile |
EP2036962A1 (fr) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Additifs pour fluides de forage à base d'eau |
EP2036963A1 (fr) * | 2007-09-14 | 2009-03-18 | Cognis Oleochemicals GmbH | Lubrifiants pour fluides de forage |
US8430936B2 (en) | 2007-11-30 | 2013-04-30 | Baker Hughes Incorporated | Stabilization of fatty oils and esters with alkyl phenol amine aldehyde condensates |
US8366907B2 (en) | 2010-08-02 | 2013-02-05 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
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CA2431749C (fr) * | 2002-07-09 | 2010-12-14 | Clariant Gmbh | Additifs lubrifiants stabilises contre l'oxydation pour huiles combustibles fortement desulfurees |
-
2003
- 2003-06-11 JP JP2003166759A patent/JP4754773B2/ja not_active Expired - Fee Related
- 2003-06-11 EP EP03013092.6A patent/EP1380633B1/fr not_active Expired - Fee Related
- 2003-06-11 ES ES03013092.6T patent/ES2464840T3/es not_active Expired - Lifetime
- 2003-06-11 US US10/458,906 patent/US20040006912A1/en not_active Abandoned
- 2003-06-11 CA CA2431748A patent/CA2431748C/fr not_active Expired - Fee Related
-
2006
- 2006-03-28 US US11/390,884 patent/US20080262252A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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CA2431748C (fr) | 2010-11-09 |
ES2464840T3 (es) | 2014-06-04 |
JP2004043800A (ja) | 2004-02-12 |
JP4754773B2 (ja) | 2011-08-24 |
US20040006912A1 (en) | 2004-01-15 |
CA2431748A1 (fr) | 2004-01-09 |
EP1380633A1 (fr) | 2004-01-14 |
US20080262252A1 (en) | 2008-10-23 |
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