EP1116780B1 - Additif polyfonctionnel pour huiles combustibles - Google Patents

Additif polyfonctionnel pour huiles combustibles Download PDF

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Publication number
EP1116780B1
EP1116780B1 EP00128082A EP00128082A EP1116780B1 EP 1116780 B1 EP1116780 B1 EP 1116780B1 EP 00128082 A EP00128082 A EP 00128082A EP 00128082 A EP00128082 A EP 00128082A EP 1116780 B1 EP1116780 B1 EP 1116780B1
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Prior art keywords
alkyl
und
carbon atoms
mol
additive
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EP1116780A1 (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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Priority claimed from DE2000100650 external-priority patent/DE10000650C2/de
Priority claimed from DE2000148682 external-priority patent/DE10048682A1/de
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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 terpolymers and amphiphilic, smear-improving additives, and 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 contain 0.5% by weight and more sulfur when burned causing the formation of sulfur dioxide. To the resulting Reducing environmental pollution becomes the sulfur content of fuel oils lowered further and further.
  • These Fuel oils are usually made by extracting them from 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.
  • R 46 is the meaning of R 1
  • R 47 is the meaning of R 1 or H or - [CH 2 -CH 2 -O-] p -H
  • R 48 may have the meaning of R 2 and p is an integer from 1 to 10, with the proviso that at least one of R 46 , R 47 and R 48 carries an OH group.
  • y- hydroxybutyric acid tallow fatty amide may be mentioned.
  • 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 ester of a carboxylic acid contained in the terpolymer of component B) 2 to 4 carbon atoms are preferably vinyl acetate or Propionate.
  • the vinyl esters of neocarboxylic acids which are furthermore contained in the terpolymer of component B) are derived from neocarboxylic acids of the formula from having a total of 8 to 15 carbon atoms.
  • R and R 1 are linear alkyl radicals.
  • the neocarboxylic acids are neononan, neodecane, neoundecan or neododecanoic acid.
  • the molar proportions of the short-chain vinyl esters in terpolymer B) are preferably at 8 to 16 mol%.
  • the molar proportions of vinyl polyvinyl esters are preferably from 1 to 8 mol%.
  • the total comonomer content is between 8 and 19, in particular between 9 and 16 mol%.
  • terpolymers according to the invention having a melt viscosity of 50 to 5000 mPa.s, preferably 30 to 1000 mPa.s and in particular 50 to 500 mPa.s, measured according to ISO 3219 (B) at 140 ° C. ,
  • terpolymers of ethylene the vinyl ester of an aliphatic linear or branched monocarboxylic acid containing 2 to 40 carbon atoms in the molecule, and Neocarbonklavinylestem starting 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'-bis (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 set at a given composition of the monomer mixture by varying the reaction parameters pressure and temperature and optionally by adding moderators.
  • Suitable moderators are hydrogen, saturated or unsaturated hydrocarbons, for example propane, aldehydes, for example propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or alcohols, for example butanol.
  • the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight, based on the monomer mixture.
  • monomer mixtures which contain, in addition to ethylene and optionally a moderator, 5 to 40% by weight, preferably 10 to 40% by weight, short-chain vinyl ester and 1 to 40% by weight. Contain% neocarboxylic acid vinyl ester.
  • 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 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. Here are some suitable ones Paraffin dispersants listed.
  • 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. V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).
  • Suitable comb polymers are, for. Fumarate / vinyl acetate copolymers (cf., EP 0 153 176 A1), copolymers of a C 6 - to C 24 - ⁇ -olefin and a NC 6 - to C 22 -alkylmaleimide (see EP-A-0 320 766 Further, esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • Paraffin dispersants or comb polymers are in each case from 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additives of the invention are suitable, the cold flow and Lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of to improve alcoholic fuels and mineral oils. They are for the Use in middle distillates particularly well suited.
  • middle distillates In particular, those mineral oils are described by distillation of crude oil be recovered and boiling in the range of 120 to 450 ° C, for example Kerosene, jet fuel, diesel and fuel oil.
  • the inventive Used additives in such middle distillates the maximum 500 ppm, in particular less than 200 ppm sulfur and in special cases less than Contain 50 ppm of sulfur.
  • the Additives of the invention are further preferably in such Middle distillates used 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C.
  • the effectiveness of the mixtures is better than from the individual components and compared to the mixtures would be expected according to the prior art.
  • the inventive additive combinations under cold blending conditions when the temperature of the oil in the additization is low, i. below 40 ° C, especially 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 can be used alone or together with other additives be, e.g. with other pour point depressants, dewaxing aids, Corrosion inhibitors, antioxidants, conductivity improvers, Sludge inhibitors, dehazem and additives to lower the cloud point.
  • Other pour point depressants e.g. with other pour point depressants, dewaxing aids, Corrosion inhibitors, antioxidants, conductivity improvers, Sludge inhibitors, dehazem and additives to lower the cloud point.
  • the addition of these additives to the oil can be used together with the invention Additive components or separately.
  • 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 .8432 .8417 .8193 S content (ppm) 290 35 54.2 478 6 HFRR-WSD ( ⁇ m) 5
  • 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 considered as an indication that the gas oil in normal cold weather is satisfactorily usable. Products with ADT values > 25 are called 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 in admixture with paraffin dispersants be used.
  • the employed Wachsdispergator (F) is a mixture of 2 parts of a terpolymer of C 14/16 - ⁇ -olefin, maleic anhydride and 2 equivalents of di-tallow Allylpolyglykol with and a part of nonylphenol-formaldehyde resin.
  • the cold flow improver polymers mentioned and, if appropriate, additionally the said wax dispersant were 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)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
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Claims (12)

  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'un composé amphiphile oléosoluble de formule 1
    Figure 00510001
    ou 2 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 des groupes hydroxyle, contenant 2 à 10 atomes de carbone, ou un groupe alkyle en C1 à C20, R1 et R2 contenant ensemble au moins 15 atomes de carbone,
    B) 5% à 95% en poids d'un terpolymère, contenant 10% à 35% en moles de motifs structurels dérivés de l'ester vinylique d'un acide carboxylique contenant 2 à 4 atomes de carbone, 1% à 15% en moles de motifs structurels dérivés de l'ester vinylique d'un acide néocarboxylique contenant 8 à 15 atomes de carbone, et le complément jusqu'à 100% en moles de motifs éthylène 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 les terpolymères du composant B) issus d'esters vinyliques d'acides néocarboxyliques contiennent des esters vinyliques d'acide néononanoïque, néodécanoïque ou néoundécanoïque.
  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 12 à 30 atomes de carbone.
  8. Huiles combustibles, contenant des distillats moyens ayant un point de distillation 95% inférieur à 370°C et une teneur en soufre d'au maximum 200 ppm et les 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, lesquelles contiennent des distillats moyens ayant un point de distillation 95% inférieur à 370°C et une teneur en soufre d'au maximum 200 ppm.
  10. Mélanges d'additifs selon l'une ou plusieurs des revendications 1 à 7 avec des résines alkylphénolformaldéhyde, le rapport de mélange de l'additif selon les revendications 1 à 7 à la résine alkylphénolformaldéhyde allant de 1:10 à 20:1.
  11. Mélanges d'additifs selon l'une ou plusieurs des revendications 1 à 7 avec des polymères en peigne de formule
    Figure 00530001
    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", 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 polymère en peigne va de 1:10 à 20:1.
  12. Mélanges d'additifs selon l'une ou plusieurs des revendications 1 à 7 avec des dispersants de paraffine, préparés au moyen d'une réaction de composés contenant un groupe acyle avec une amine de formule NR6R7R8, dans laquelle R6, R7 et R8 peuvent être identiques ou différents et dans laquelle au moins un des ces groupes représente un groupe alkyle en C8 à C36, cycloalkyle en C6 à C36 ou alcényle en C8 à C36 et les groupes restants représentent un atome d'hydrogène, un groupe alkyle en C1 à C36, alcényle en C2 à C36, cyclohexyle ou un groupe de formule -(A-O)x-E ou -(CH2)n-NYZ, dans lesquelles A représente un groupe éthylène ou propylène, x représente un nombre de 1 à 50, E représente un atome d'hydrogène, un groupe alkyle en C1 à C30, cycloalkyle en C5 à C12 ou aryle en C6 à C30 et n vaut 2, 3 ou 4, et Y et Z représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe alkyle en C1 à C30 ou un groupe -(A-O)x.
EP00128082A 2000-01-11 2000-12-21 Additif polyfonctionnel pour huiles combustibles Expired - Lifetime EP1116780B1 (fr)

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DE10000650 2000-01-11
DE2000100650 DE10000650C2 (de) 2000-01-11 2000-01-11 Mehrfunktionelles Additiv für Brennstofföle
DE2000148682 DE10048682A1 (de) 2000-09-30 2000-09-30 Mehrfunktionelles Additiv für Brennstofföle
DE10048682 2000-09-30

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US20040060225A1 (en) 2004-04-01
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CA2331028C (fr) 2009-11-17
DE50011064D1 (de) 2005-10-06
EP1116780A1 (fr) 2001-07-18
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US20020002793A1 (en) 2002-01-10
US7435271B2 (en) 2008-10-14

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