EP1446464B1 - Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol - Google Patents

Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol Download PDF

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EP1446464B1
EP1446464B1 EP02802985A EP02802985A EP1446464B1 EP 1446464 B1 EP1446464 B1 EP 1446464B1 EP 02802985 A EP02802985 A EP 02802985A EP 02802985 A EP02802985 A EP 02802985A EP 1446464 B1 EP1446464 B1 EP 1446464B1
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EP1446464A2 (fr
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Matthias Krull
Martina Hess
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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
    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/18—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
    • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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

Definitions

  • the invention relates to additives for low-sulfur mineral oil distillates with improved cold flowability and paraffin dispersion comprising an ester an alkoxylated polyol and an alkylphenol-aldehyde resin, additized Fuel oils and the use of the additive.
  • Crude oils and middle distillates obtained by the distillation of crude oils such as gas oil, Diesel oil or fuel oil contain different depending on the origin of the crude oils Amounts of n-paraffins which, when the temperature is lower than crystallize platelet-shaped crystals and partially with the inclusion of oil agglomerate.
  • this crystallization and agglomeration it comes to a Deterioration of the flow properties of the oils or distillates, whereby at Extraction, transport, storage and / or use of mineral oils and Mineral oil distillates may occur disorders.
  • the crystallization phenomenon can be especially prevalent in winter Deposits on the pipe walls, in individual cases, e.g. at standstill one Pipeline, even lead to their complete constipation.
  • Typical flow improvers for crude oils and middle distillates are co-and Terpolymers of ethylene with carboxylic esters of vinyl alcohol.
  • Another object of flow improver additives is the dispersion of the Paraffin crystals, i. the delay or prevention of sedimentation of the Paraffin crystals and thus the formation of a paraffin-rich layer on the ground from storage containers.
  • EP-A-0 061 895 discloses cold flow improvers for mineral oil distillates containing esters, ethers or mixtures thereof.
  • the esters / ethers contain two linear saturated C 10 to C 30 alkyl groups and one polyoxyalkylene group at 200 to 5000 g / mol.
  • EP 0 973 848 and EP 0 973 850 disclose mixtures of esters alkoxylated Alcohols with more than 10 C atoms and fatty acids with 10 - 40 C atoms in Combination with ethylene copolymers as flow improvers.
  • EP-A-0 935 645 discloses alkylphenol-aldehyde resins as lubricating additives Addition in low-sulfur middle distillates.
  • EP-A-0857776 and EP 1088045 disclose methods for improving the Flowability of paraffin-containing mineral oils and mineral oil distillates Addition of ethylene copolymers and alkylphenol-aldehyde resins as well optionally further, nitrogen-containing paraffin dispersants.
  • an additive in addition to alkylphenol-aldehyde resins also contains certain esters of alkoxylated polyols, a represents particularly good cold flow improver for low-sulfur fuel oils.
  • the invention thus provides additives for middle distillates with a maximum 0.05% by weight of sulfur content, containing at least one fatty acid ester alkoxylated polyols having at least 3 OH groups (A) and at least one Alkylphenol-aldehyde resin (C).
  • Another object of the invention are middle distillates with maximum 0.05% by weight of sulfur containing an additive containing at least one Fatty acid esters of alkoxylated polyols having at least 3 OH groups (A) and contains at least one alkylphenol-aldehyde resin (C).
  • Another object of the invention is the use of an additive, containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one alkylphenol-aldehyde resin (C), for Improvement of cold flow properties and paraffin dispersion of Middle distillates with a maximum of 0.05 wt .-% sulfur content.
  • Another object of the invention is a method for improving the Cold flow properties of middle distillates with a maximum of 0.05% by weight Sulfur content by adding to the middle distillates an additive containing at least one fatty acid ester of alkoxylated polyols having at least 3 OH groups (A) and at least one alkylphenol-aldehyde resin (C).
  • the esters (A) are derived from polyols having 3 or more OH groups, in particular of glycerol, trimethylolpropane, pentaerythritol and the like condensation-accessible oligomers having from 2 to 10 monomer units, such as e.g. Polyglycerol.
  • the polyols are generally containing from 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50 moles of alkylene oxide per mole of polyol implemented.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and Butylene oxide.
  • the alkoxylation is carried out by known methods.
  • the fatty acids which are suitable for the esterification of the alkoxylated polyols preferably 8 to 50, in particular 12 to 30, especially 16 to 26 C-atoms.
  • Suitable fatty acids are, for example, lauric, tridecane, myristic, Pentadecane, palmitic, margarine, stearic, isostearic, arachinic and behenic acid, Oil and erucic acid, palmitoleic, myristolein, ricinoleic acid, and natural Fats and oils derived fatty acid mixtures.
  • Bevorzgte Fatty acid mixtures contain more than 50% fatty acids with at least 20 C atoms.
  • esterification can also be based on reactive Derivatives of fatty acids such as esters with lower alcohols (e.g., methyl or Ethyl ester) or anhydrides.
  • polybasic carboxylic acids dimer fatty acids, alkenylsuccinic acids and aromatic polycarboxylic acids and derivatives thereof such as anhydrides and C 1 - to C 5 -esters.
  • Alkenylsuccinic acid and its derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred.
  • Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride.
  • the polybasic carboxylic acids are preferably used here to lower levels of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.
  • Ester and fatty acid are used for esterification based on the content Hydroxyl groups on the one hand and carboxyl groups on the other hand in the ratio 1.5: 1 to 1: 1.5 used, preferably 1.1: 1 to 1: 1.1, in particular equimolar.
  • the paraffin-dispersing effect is particularly pronounced when with a Acid excess of up to 20 mol%, especially up to 10 mol%, in particular to to 5 mol% is worked.
  • the esterification is carried out by conventional methods. Has proven particularly useful the implementation of Polyolalkoxilat with fatty acid, optionally in the presence of catalysts such as para-toluenesulfonic acid, C 2 - to C 50 -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers.
  • catalysts such as para-toluenesulfonic acid, C 2 - to C 50 -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers.
  • the separation of the water of reaction can be carried out by distillation by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or higher boiling mixtures such as ®Shellsol A, Shellsol B, Shellsol AB or Solvent Naphtha.
  • the esterification is preferably carried out completely, ie for the esterification 1.0 to 1.5 moles of fatty acid are used per mole of hydroxyl groups.
  • the acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.
  • alkylphenol-aldehyde resins (C) contained in the additive according to the invention are known in principle and, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351 et seq described.
  • the alkyl radicals of the o- or p-alkylphenols have 1 to 50, preferably 4 to 20, in particular 6 to 12 Carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl as well as tetrapropenyl, pentapropenyl and polyisobutenyl.
  • the Alkylphenol-aldehyde resin may also contain up to 50 mole% phenol units.
  • alkylphenol-aldehyde resin the same or different alkylphenols be used.
  • the aliphatic aldehyde in the alkylphenol-aldehyde resin has 1-10, preferably 1-4, carbon atoms and may have other functional groups as carry aldehyde or carboxyl groups. It is preferably formaldehyde.
  • the Molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400 - 5000 g / mol. The prerequisite here is that the resins are oil-soluble.
  • the preparation of the alkylphenol-aldehyde resins is carried out in a known manner basic catalysis, resulting in resol-type condensation products, or by acid catalysis to produce novolac-type condensation products.
  • the condensates obtained according to both types are for the invention Compositions suitable.
  • the condensation is in the presence of acid catalysts.
  • alkylphenol-aldehyde resins are a bifunctional o- or p-alkylphenol having 1 to 50 carbon atoms, preferably 4 to 20, in particular 6 to 12 C atoms per alkyl group, or mixtures thereof and an aliphatic one Aldehyde having 1 to 10 carbon atoms reacted with each other, wherein per mol Alkylphenol compound about 0.5 to 2 mol, preferably 0.7 to 1.3 mol and In particular, equimolar amounts of aldehyde can be used.
  • Suitable alkylphenols are, in particular, C 4 -C 50 -alkylphenols, for example o- or p-cresol, n-, sec- and tert-butylphenol, n- and i-pentylphenol, n- and isohexylphenol, n- and - iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyis (isobutenyl) phenol.
  • C 4 -C 50 -alkylphenols for example o- or p-cresol, n-, sec- and tert-butylphenol, n- and i-p
  • the alkylphenols are preferably para-substituted. They are preferably too at most 7 mol%, in particular at most 3 mol% with more than one Substituted alkyl group.
  • aldehydes are formaldehyde, acetaldehyde, butyraldehyde and glutaraldehyde, preferred is formaldehyde.
  • the formaldehyde may be in the form of paraformaldehyde or in the form of a preferably 20 to 40% strength by weight aqueous formalin solution are used. 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, and in the presence of one with water an azeotrope-forming organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof.
  • the reaction mixture is on a Temperature of 90 to 200 ° C, preferably 100 - 160 ° C heated, the Resulting water of reaction during the reaction by azeotropic Distillation is removed.
  • Solvents that are in the conditions of Condensation does not cleave protons after the condensation reaction stay in the products.
  • the resins can be used directly or after neutralization of the Catalyst can be used, optionally after further dilution of Solution with aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. 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 e.g. Gasoline fractions, kerosene, decane, Pentadecane, toluene, xylene, ethyl
  • the alkylphenol resins can then optionally by reaction with 1 to 10, especially 1 to 5 moles of alkylene oxide such as ethylene oxide, propylene oxide or Butylene oxide per phenolic OH group are alkoxylated.
  • the additives or fuel oils according to the invention are added.
  • preferred embodiments are also fuel oils according to the invention, the ethylene copolymers (B), Paraffin dispersants (D) and / or comb polymers contain, and the use of additives according to the invention, which ethylene copolymers (B), Paraffin dispersants (D) and / or comb polymers contain, and the appropriate procedures.
  • Copolymer B) is preferably an ethylene copolymer having an ethylene content of 60 to 90 mol% and a comonomer content of 10 to 40 mol%, preferably 12 to 18 mol%.
  • Suitable comonomers are vinyl esters of aliphatic carboxylic acids having 2 to 15 carbon atoms.
  • Preferred vinyl esters for copolymer B) are vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, here in particular neononan, neodecane and neoundecanoic acid.
  • an ethylene-vinyl acetate copolymer particularly preferred are an ethylene-vinyl acetate copolymer, an ethylene-vinyl propionate copolymer, an ethylene-vinyl acetate-vinyl octanoate terpolymer, an ethylene-vinyl acetate-vinyl-2-ethylhexyl terpolymer, an ethylene-vinyl acetate-neononanoic acid vinyl ester terpolymer, or an ethylene -Vinylacetat-neodecanoate terpolymer.
  • Preferred acrylic acid esters are acrylic esters having alcohol radicals of from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • the copolymers may contain up to 5% by weight of other comonomers.
  • Such comonomers may be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C 1 to C 20 alkyl radicals, isobutylene and olefins.
  • Preferred as higher olefins are hexene, isobutylene, octene and / or diisobutylene.
  • Suitable comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Particularly preferred are ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers.
  • the copolymers have melt viscosities at 140 ° C of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
  • the copolymers (B) are prepared by the usual copolymerization methods such as for example suspension polymerization, solvent polymerization, Gas phase polymerization or high-pressure mass polymerization produced. Preference is given to the high-pressure mass polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350, in particular 100 to 250 ° C.
  • the reaction of Monomers Are Generated by Radical Initiators (Radical Chain Starters) initiated. This class of substance includes e.g.
  • Oxygen, hydroperoxides, Peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, Dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, Di (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of from 0.01 to 20% by weight, preferably 0.05 to 10 wt .-%, based on the monomer mixture, used.
  • High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene may be included in the reaction mixture.
  • the solvent-free operation is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet as well supplied via one or more side branches.
  • the Monomer streams may be composed differently (EP-A-0 271 738).
  • Paraffin dispersants, resins or comb polymers are each 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • the additive components of the invention may be mineral oils or Mineral oil distillates are added separately or in mixture.
  • the solution or dispersion generally contains 5-90, preferably 5-75 wt .-% of Additive or additive mixture.
  • Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Benzine 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.
  • polar solubilizers such as 2-ethylhexanol, Decanol, iso-decanol or iso-tridecanol.
  • Mineral oils or mineral oil distillates contain from 0.001 to 2, preferably from 0.005 to 0.5 wt .-% of the additives, based on the mineral oil or mineral oil distillate.
  • the additives according to the invention are particularly suitable, the Cold flow properties of animal, vegetable or mineral oils improve. At the same time they improve below the cloud point Dispersion of the precipitated paraffins. They are for use in Middle distillates particularly well suited. As middle distillates one calls in particular those mineral oils obtained by distillation of crude oil and boiling in the range of 120 to 450 ° C, for example, kerosene, jet fuel, Diesel and heating oil. Preferably, the additives of the invention in low-sulfur middle distillates used 350 ppm sulfur and less, more preferably less than 200 ppm sulfur and especially less contain as 50 ppm of sulfur.
  • the additives of the invention are furthermore preferably used in such middle distillates, the 95% distillation points below 365 ° C, especially 350 ° C and in special cases below 330 ° C and in addition to high levels of paraffins having 18 to 24 carbon atoms only small amounts of paraffins with chain lengths of 24 and more carbon atoms contain. They can also be used as components in lubricating oils become.
  • the mineral oils or mineral oil distillates may also be other common Additives such as dewaxing aids, corrosion inhibitors, Antioxidants, lubricity additives, sludge inhibitors, cetane improvers, Detergent additives, dehazers, conductivity improvers or dyes.
  • Additives such as dewaxing aids, corrosion inhibitors, Antioxidants, lubricity additives, sludge inhibitors, cetane improvers, Detergent additives, dehazers, conductivity improvers or dyes.
  • esters A were used as a 50% solution in aromatic solvent (EO stands for ethylene oxide, PO stands for propylene oxide): Table 1: Characterization of the esters used (constituent A) Main components of fatty acids acid number OH number additive polyol alkoxylation C 18 C 20 C 22 [mg KOH / g] [mg KOH / g] A1 glycerin 22 mol EO 2 7 88 7 13 A2 glycerin 22 mol EO 95% 5 4 A3 glycerin 22 mol EO 37 10 48 1 2 A4 glycerin 16 mol PO 37 10 48 7 9 A5 glycerin 16 mol PO 2 7 88 5 7 A6 glycerin 24 mol PO 37 10 48 8th 11 A7 glycerin 10 mol EO 2 7 88 7 9 A8 glycerin 30 mol EO 2 7 88 2 4 A9 glycerin 40 mol EO 2 7 88 12 10 A10 g
  • the additives are used to improve handling as 50% solutions used in solvent naphtha or kerosene.
  • the boiling characteristics are determined according to ASTM D-86, the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015. Characteristics of the test oils Test oil 1 Test oil 2 Test oil 3 Test oil 4 Start of boiling [° C] 169 200 174 241 20% [° C] 211 251 209 256 90% [° C] 327 342 327 321 95% [° C] 344 354 345 341 Cloud Point [° C] -9.0 -4.2 -6.7 -8.2 CFPP [° C] -10 -6 -8th -10 sulfur content 33 ppm 35 ppm 210 ppm 45 ppm
  • Table 4 describes the superior efficiency of the inventive additives in comparison with the prior art together with ethylene copolymers for mineral oils and mineral oil distillates by means of the CFPP test (Cold Filter Plugging Test according to EN 116).
  • the paraffin dispersion in middle distillates was determined in the short sediment test as follows: 150 ml of the middle distillates added with the additive components indicated in the table were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the overlying oil phase were determined and assessed visually.
  • a small amount of sediment with simultaneously homogeneous turbid oil phase or a large sediment volume with a clear oil phase show a good paraffin dispersion.
  • the lower 20% by volume were isolated and the cloud point was determined according to ISO 3015. Only a small deviation of the cloud point of the lower phase (CP KS ) from the blank value of the oil shows a good paraffin dispersion.
  • CFPP activity in test oil 1 The CFPP activity of the esters A according to the invention was measured in combination with equal amounts of C and D in test oil 1 as follows: A C D B3 in ppm 50 75 100 example 1 50 ppm A1 50 ppm C1 50 ppm D2 -29 -31 -30 Example 2 50 ppm A11 50 ppm C2 50 ppm D1 -27 -30 -30 Example 3 50 ppm A7 50 ppm C1 50 ppm D2 -17 -28 -29 Example 4 50 ppm A12 50 ppm C1 50 ppm D2 -19 -31 -29 Example 5 50 ppm A8 50 ppm C1 50 ppm D2 -21 -29 -29 Example 6 50 ppm A9 50 ppm C1 50 ppm D2 -18 -24 -29 Example 7 50 ppm A2 50 ppm C1 50 ppm D2 -26 -29 -28 Example 8 50 ppm A
  • Test oil 3 (CP -6.7 ° C) A C Sediment [vol.%] Appearance oil phase CFPP [° C] CP KS [° C]
  • Example 21 100 ppm A1 50 ppm C1 0 cloudy -23 -5.9
  • Example 22 100 ppm A1 50 ppm C2 7 cloudy -24 -3.3
  • Example 23 100 ppm A2 50 ppm C2 10 cloudy -21 -2.4
  • Example 24 100 ppm A1 50 ppm C3 20 cloudy -21 -0.8
  • Example 25 50 ppm A2 100 ppm C1 20 cloudy -26 -1.4
  • Example 26 100 ppm A3 50 ppm C1 10 cloudy -28 -1.4
  • Example 27 50 ppm A3 100 ppm C1 0 cloudy -28 -5.3
  • Example 28 100 ppm A4 100 ppm C1 7 cloudy -21 -3.6
  • Example 29 50 ppm A4 100
  • Test oil 4 (CP -8,2 ° C) A C Sediment [vol.%] Appearance oil phase CFPP [° C] CP KS [° C]
  • Example 40 100 ppm A1 100 ppm C1 0 cloudy -24 -6.3
  • Example 41 100 ppm A1 100 ppm C1 0 cloudy -24 -7.5
  • Example 42 50 ppm A3 100 ppm C1 0 cloudy -24 -5.4
  • Example 43 50 ppm A3 100 ppm C1 0 cloudy -28 -5.3
  • Example 44 100 ppm A5 50 ppm C1 50 cloudy -23 -3.3
  • Example 45 100 ppm A5 100 ppm C1 0 cloudy -23 -5.5
  • Example 46 50 ppm A5 100 ppm C1 70 cloudy -24 -4.3
  • Example 47 100 ppm A14 50 ppm C1 16 clear -18 -1.1
  • Example 48 150 ppm A1

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Claims (13)

  1. Distillats moyens ayant une teneur maximale en soufre de 0,05 % en poids, contenant au moins un ester d'acide gras de polyols alcoxylés ayant au moins 3 groupes OH (A) et au moins une résine d'alkylphénolaldéhyde (C).
  2. Distillats moyens selon la revendication 1, dans lesquels le polyol alcoxylé (A) dérive d'un polyol ayant au moins trois groupes OH, qui a été mis à réagir avec 1 à 100 moles d'oxyde d'alkylène.
  3. Distillats moyens selon la revendication 1 et/ou 2, dans lesquels le polyol alcoxylé (A) est estérifié avec un acide gras ayant de 8 à 50 atomes de carbone.
  4. Distillats moyens selon l'une ou plusieurs des revendications 1 à 3, dans lesquels le polyol alcoxylé (A) est estérifié par un mélange d'au moins un acide gras ayant de 8 à 50 atomes de carbone et au moins un acide polycarboxylique soluble dans les graisses.
  5. Distillats moyens selon l'une ou plusieurs des revendications 1 à 4, dans lesquels le polyol alcoxylé (A) dérive du glycérol.
  6. Distillats moyens selon l'une ou plusieurs des revendications 1 à 5, dans lesquels l'ester d'acide gras (A) présente un indice d'hydroxyle inférieur à 15 mg KOH/g.
  7. Distillats moyens selon l'une ou plusieurs des revendications 1 à 6, dans lesquels les groupes alkyle de la résine d'alkylphénol-aldéhyde (C) ont de 1 à 50 atomes de carbone.
  8. Distillats moyens selon l'une ou plusieurs des revendications 1 à 7, dans lesquels la résine d'alkylphénol-aldéhyde (C) dérive d'au moins un aldéhyde ayant de 1 à 10 atomes de carbone.
  9. Distillats moyens selon l'une ou plusieurs des revendications 1 à 8, qui contiennent en outre un copolymère de l'éthylène.
  10. Distillats moyens selon la revendication 9, dans lesquels le copolymère de l'éthylène contient au moins un ester vinylique insaturé d'un acide carboxylique aliphatique ayant de 2 à 15 atomes de carbone.
  11. Distillats moyens selon la revendication 9 et/ou 10, dans lesquels le copolymère de l'éthylène contient, outre de l'éthylène, 10 à 40 % en moles de comonomères.
  12. Distillats moyens selon l'une ou plusieurs des revendications 1 à 11, qui contiennent en outre un dispersant azoté polaire de paraffines, contenant de sels d'amine et/ou d'amide d'amines grasses secondaires ayant de 8 à 36 atomes de carbone.
  13. Utilisation d'un additif contenant un ester d'acide gras de polyols alcoxylés ayant au moins 3 groupes OH (A) et au moins une résine d'alkylphénolaldéhyde (C), pour améliorer les propriétés d'écoulement à froid et de dispersion des paraffines dans des distillats moyens ayant une teneur maximale en soufre de 0,05 % en poids.
EP02802985A 2001-11-14 2002-11-02 Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol Expired - Lifetime EP1446464B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10155747A DE10155747B4 (de) 2001-11-14 2001-11-14 Additive für schwefelarme Mineralöldestillate, umfassend einen Ester eines alkoxylierten Polyols und ein Alkylphenol-Aldehydharz
DE10155747 2001-11-14
PCT/EP2002/012235 WO2003042338A2 (fr) 2001-11-14 2002-11-02 Additifs pour distillats de petrole pauvres en soufre, contenant un ester d'un polyol alkoxyle et une resine aldehyde alkyle phenol

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EP1446464A2 EP1446464A2 (fr) 2004-08-18
EP1446464B1 true EP1446464B1 (fr) 2005-07-27

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JP (1) JP2005509086A (fr)
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DE (2) DE10155747B4 (fr)
ES (1) ES2243799T3 (fr)
WO (1) WO2003042338A2 (fr)

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WO2005040315A1 (fr) * 2003-10-22 2005-05-06 Leuna Polymer Gmbh Melange d'additifs utilise comme constituant d'une formulation a base d'huile minerale
JP5033422B2 (ja) * 2003-10-22 2012-09-26 ロイナ ポリマー ゲーエムベーハー 鉱物油組成物の成分としての添加剤混合物
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DE50203784D1 (de) 2005-09-01
ES2243799T3 (es) 2005-12-01
US7377949B2 (en) 2008-05-27
KR101072787B1 (ko) 2011-10-14
WO2003042338A2 (fr) 2003-05-22
JP2005509086A (ja) 2005-04-07
DE10155747B4 (de) 2008-09-11
WO2003042338A3 (fr) 2003-10-09
KR20050042255A (ko) 2005-05-06
DE10155747A1 (de) 2003-05-28
EP1446464A2 (fr) 2004-08-18
US20050000152A1 (en) 2005-01-06

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