WO2024037904A1 - Composition pour réduire la cristallisation de cristaux de paraffine dans des combustibles - Google Patents

Composition pour réduire la cristallisation de cristaux de paraffine dans des combustibles Download PDF

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WO2024037904A1
WO2024037904A1 PCT/EP2023/071774 EP2023071774W WO2024037904A1 WO 2024037904 A1 WO2024037904 A1 WO 2024037904A1 EP 2023071774 W EP2023071774 W EP 2023071774W WO 2024037904 A1 WO2024037904 A1 WO 2024037904A1
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vinyl
acid
mixture according
meth
copolymer
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English (en)
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Ivette Garcia Castro
Aleksandra Martyna GAJDA
Irene Troetsch-Schaller
Martina SCHOEMER
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Basf Se
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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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
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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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/04—High pressure, i.e. P > 50 MPa, 500 bars or 7250 psi
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
    • 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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • 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
    • C10L1/2362—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing nitrile 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel

Definitions

  • the present invention relates to a composition of copolymers for reducing the crystallization of paraffin crystals in fuels and/or for improving the cold flow properties of fuel oils and/or for improving the filterability of containing fuel oils, as well as fuel oils containing such a composition.
  • Middle distillate fuels from fossil origin especially gas oils, diesel oils or light heating oils that are obtained from petroleum, have different paraffin contents depending on the origin of the crude oil.
  • solid paraffins precipitate at the cloud point (“CP”).
  • CP cloud point
  • the platelet-shaped n-paraffin crystals form a kind of "house of cards” structure and the middle distillate fuel stagnates, although the majority of it is still liquid.
  • Due to the precipitated n-paraffins in the temperature range between the cloud point (cloud point) and pour point (“PP”) the flowability of the middle distillate fuels is significantly impaired; The paraffins clog filters and cause an uneven or completely interrupted fuel supply to the combustion units. Similar problems occur with light heating oils.
  • Ethylene-vinyl acetate copolymers are widely used additives for fuel oils, as known, for example, from EP 1433836 for certain fuel oils, which also contain polymerized vinyl alkanoates of branched Cs-Ci9 carboxylic acids.
  • EVA copolymers in a mixture with copolymers of maleic anhydride and ⁇ -olefins with 10 to 20 carbon atoms, reacted with primary or secondary amines with Cs to Ci6 alkyl radicals.
  • the amines are incorporated via amide or imide bonds.
  • the length of the a-olefin and alkyl residues of the amine must meet a certain ratio in order to be suitable as a cold flow improver for fuel oils.
  • the ratio of amine to anhydride is preferably from 1.0 to 2.0 mol per mol of anhydride. It is also expressly stated that shorter and longer alkyl chains than Cs to C16 on the amines do not contribute to the effectiveness of the additives.
  • copolymers from components (A), (B), (C) and optionally (D) and (E) with a molar incorporation ratio of (A): (B): (C): (D ) from 1: 0.5 to 2.0: 0.5 to 2.0: 0 to 0.1 known. These copolymers therefore have a high content of C3 to C20 alkyl esters of acrylic acid or methacrylic acid (C).
  • copolymers from components (A), (B), (C) and optionally (D) and (E) with a molar incorporation ratio of (A): (B): (C): (D) from 1:0.5 to 2.0:0 to less than 0.5:0 to 0.1.
  • These copolymers therefore have an optional low content of C3 to C2o alkyl esters of acrylic acid or methacrylic acid (C).
  • C cloud point
  • CFPP cold filter plugging point
  • the task was to provide improved products which further reduce this undesirable tendency of middle distillate fuels to paraffin sedimentation.
  • Another subject of the present invention are fuel oils containing such mixtures.
  • the copolymer (I) is at least one copolymer made up of -- (la) ethylene -- (Ib) vinyl acetate
  • copolymers for example two to three or preferably two.
  • the copolymer (I) is particularly preferably a copolymer.
  • the copolymer (I) contains at least one vinyl Ce-C2o alkanoate (Ic) and can optionally contain at least one C6-C20 alkyl (meth)acrylate (Id) and / or optionally additionally contain further monomers other than (la) to (Id).
  • At least one monomer (Ic) is incorporated into the copolymer (I), so that it is at least a terpolymer.
  • Monomers (Ic) are vinyl esters of linear or branched, preferably branched C6-C20 carboxylic acids, preferably of branched Cs-Cis carboxylic acids, particularly preferably of branched Cs-Ci6 carboxylic acids and very particularly preferably of branched C9-C16 carboxylic acids.
  • branched carboxylic acids have a branch in the alpha position to the carboxyl group.
  • Particularly suitable monomers (Ic) are organic molecules with one or more polymerizable vinyl groups, for example vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl 3-propylheptanoate, vinyl ester of nonanoic acid (“Veova9”), neodecanoic acid (“VeovalO”), vinyl decanoate, vinyl dodecanoate, vinyl tridecanoate, vinyl isotridecanoate, vinyl tetradecanoate, vinyl pentadecanoate, vinyl hexadecanoate and vinyl octadecanoate.
  • vinyl hexanoate vinyl 2-ethylhexanoate
  • vinyl octanoate vinyl 3-propylheptanoate
  • vinyl ester of nonanoic acid (“Veova9")
  • neodecanoic acid VeovalO”
  • vinyl decanoate vinyl dodecanoate
  • it is vinyl hexanoate, vinyl 2-ethylhexanoate or vinyl 3-propylheptanoate.
  • the monomer (Ic) is vinyl ester of the Versatic acids with 9 to 13 carbon atoms, preferably 9 to 11 and particularly preferably 9 or 10.
  • Versatic acids have a quaternary alpha carbon atom adjacent to the carboxyl group, which has a methyl group and two other alkyl groups.
  • Versatic acids are mixtures of isomers, for example Versatic acid 10 (CAS number 26896-20-8) is usually a mixture of the isomers 2,2,3,5-tetramethylhexanoic acid
  • the monomers (Id) are C6-C2o-alkyl (meth)acrylates, where the corresponding Ce-C2o-alkanols can be linear or branched, preferably Cs-Cis-alkyl (meth)acrylates, particularly preferably C8 -Ci6-alkyl (meth)acrylates, very particularly preferably C8-Ci4-alkyl (meth)acrylates and in particular C8-Ci2-alkyl (meth)acrylates.
  • the acrylic acid esters are preferred over the respective methacrylic acid esters.
  • C6-C2o-alkyl (meth)acrylates are (meth)acrylic acid esters of CB to C2o-alkanols, preferably of n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, n-decanol, 2-propylheptanol, n-Dodecanol (lauryl alcohol), tridecanol isomer mixtures, n-tetradecanol, n-hexadecanol, heptadecanol isomer mixtures, n-octadecanol and n-eicosanol. Particularly preferred are 2-ethylhexyl acrylic acid and 2-propylheptyl acrylic acid.
  • N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams, (Ie4) ethylenically unsaturated aromatics
  • vinyl ethers (Ie1) are vinyl ethers of Ci- to Ci2-alkanols, preferably vinyl ethers of methanol, ethanol, /so-propanol, n-propanol, n-butanol, /so-butanol, se-butanol, tert-butanol, n -Hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
  • Examples of monomers (Ie2) are allyl alcohols and allyl ethers of C2 to Ci2 alkanols, preferably allyl ethers of methanol, ethanol, /so-propanol, n-propanol, n-butanol, /so-butanol, sec-butanol, te/Y -Butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
  • Examples of vinyl compounds (Ie3) of heterocycles containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.
  • Preferred compounds (Ie3) are N-vinyl amides or N-vinyl lactams:
  • N-vinylamides or N-vinyllactams are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.
  • ethylenically unsaturated aromatics are styrene and a-methylstyrene.
  • Examples of ⁇ , ⁇ -ethylenically unsaturated nitriles (Ie5) are acrylonitrile and methacrylonitrile.
  • Examples of (meth)acrylamides (Ie6) are acrylamide and methacrylamide.
  • Examples of allylamines (Ie7) are allylamine, dialkylallylamine and trialkylallylammonium halide.
  • Preferred monomers (le) are the vinyl ethers, N-vinyl compounds and/or ethylenically unsaturated aromatics mentioned, particularly preferably vinyl ethers and/or ethylenically unsaturated aromatics, very particularly preferably ethylenically unsaturated aromatics.
  • Copolymers (I) are typically composed as follows:
  • no monomers (Id) are present.
  • no monomers (le) are present.
  • no monomers (Id) and no monomers (le) are present.
  • Typical molecular weights of the copolymers (I) are from 1000 to 20,000 g/mol, preferably from 1000 to 10,000 and particularly preferably 1000 to 6000 g/mol.
  • the copolymer (II) is obtainable by copolymerization of
  • (D) optionally one or more further copolymerizable monomers that are different from the monomers (A), (B) and (C), with a molar incorporation ratio of (A): (B): (C): (D) from 1: 0.5 to 2.0: 0 to 2.0: 0 to 0.1 followed by reaction with at least one dialkylamine (E), whereby the two alkyl radicals of the at least one dialkylamine (E) are independently alkyl radicals having at least 17 to 30 carbon atoms.
  • E dialkylamine
  • the monomer (A) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably exactly one unsaturated dicarboxylic acid or its derivatives.
  • derivatives are understood to mean the relevant anhydrides in monomeric or polymeric form, mono- or dialkyl esters, preferably mono- or di-Ci-C4-alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, mixed esters, preferably mixed esters with different Ci-C4 alkyl components, particularly preferably mixed methyl ethyl esters, and
  • Mono- and diamides as well as imides which are obtainable by reacting the unsaturated dicarboxylic acid with primary amines or secondary amines, preferably Ci-C 3 o-alkylamines or di-Ci-Cso-alkylamines.
  • the derivatives are preferably anhydrides in monomeric form or di-Ci-C4-alkyl esters, particularly preferably anhydrides in monomeric form.
  • the derivatives are diamides or monoamides, preferably monoamides, which are obtainable by reacting the unsaturated dicarboxylic acid with dialkylamines (E), the alkyl radicals of which independently have at least 17 to 30 carbon atoms.
  • E dialkylamines
  • Ci-C4-alkyl is understood to mean methyl, ethyl, /so-propyl, n-propyl, n-butyl, iso-butyl, se/r-butyl and /e/7-butyl, preferably methyl and ethyl , particularly preferably methyl.
  • the unsaturated dicarboxylic acid is those dicarboxylic acids or their derivatives in which both carboxyl groups are conjugated with the ethylenically unsaturated double bond.
  • maleic acid fumaric acid, 2-methylmaleic acid, 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid and particularly preferably maleic acid and its derivatives.
  • the monomer (A) is maleic anhydride.
  • the monomer (B) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one a-olefin with from at least 6 up to and including 30 carbon atoms.
  • the a-olefins (B) preferably have at least 8, particularly preferably at least 10, carbon atoms.
  • the ⁇ -olefins (B) preferably have up to and including 30, particularly preferably up to and including 22 and very particularly preferably up to and including 16 carbon atoms.
  • the determination of the number of carbon atoms should be based on the statistical average of the numbers of carbon atoms of the olefins contained in the mixture. As a result, a mixture of 50 mol% C22 olefin and 50 mol% Ci6 olefin has a statistical average of 19 carbon atoms.
  • ⁇ -olefins in the mixture have the number of carbon atoms specified above, preferably at least 90 mol%, particularly preferably at least 95 mol% and very particularly preferably at least 98 mol% and in particular 100 mol%.
  • the ⁇ -olefins can preferably be linear or branched, preferably linear, 1-alkenes.
  • Examples include 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene , 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene and 1-triacontene, of which 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene are preferred and 1-dodecene is particularly preferred.
  • the optional monomer (C) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one C4 to C22 alkyl ester of acrylic acid or methacrylic acid, preferably acrylic acid , or a mixture of such alkyl esters.
  • the alkyl radical can be straight-chain or branched.
  • Suitable C4 to C22 alkyl esters of acrylic acid or methacrylic acid, preferably acrylic acid, for component (C) are preferably the esters of acrylic and methacrylic acid with C4 to C22 alkanols, preferably with C4 to cis alkanols, particularly preferably with Cs to Cis alkanols, very particularly preferably C10 to Cu alkanols and in particular Ci2 alkanols, for example with n-propanol, iso-propanol, n-butanol, see.
  • the alkanols are branched C13 or Cn alkanols or mixtures thereof, which have an average degree of branching according to the iso index of 1.2 to 3.0, in particular 1.7 to 2.5 .
  • Such alkanols or mixtures thereof are obtainable by oligomerization of C4 hydrocarbon streams, in particular homogeneously or heterogeneously catalyzed oligomerization of technical C4 streams from 10 to 90% by weight of butane, 10 to 90% by weight of linear butenes (butene-1, cis - and trans-butene-2) as well as 1 to 5% by weight of isobutene, for example from raffinate II.
  • a typical heterogeneous catalyst for this contains nickel.
  • the oligomerization is usually carried out at temperatures of 30 to 280 ° C and pressures of 10 to 300 bar. Such oligomerization reactions are described, for example, in WO 99/25668.
  • the oligomerization products are then hydroformylated and hydrogenated, thus yielding the alkanols or alkanol mixtures mentioned.
  • Component (C) is preferably n-decyl (meth) acrylate, 2-propylheptyl (meth) acrylate, n-undecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth). )acrylate, isotridecyl (meth)acrylate, n-tetradecyl (meth)acrylate or behenyl (meth)acrylate, particularly preferably n-dodecyl (meth)acrylate or n-tetradecyl (meth)acrylate or mixtures thereof and very particularly preferably the respective acrylates.
  • the optional further monomers (D), which are other than the monomers (A), (B) and (C), are preferably selected from the group consisting of cycloaliphatic (meth)acrylates (D1), (Meth) Acrylates of polyalkylene glycol monoalkyl ethers (D2), vinyl alkanoates (D3), allyl compounds (D4), vinyl ethers (D5), N -vinyl lactams (D6), N-vinyl imidazoles (D7), ethylenically unsaturated aromatics (D8), sulfur dioxide (D9 ), ethylenically unsaturated nitriles (D10) and esters of acrylic acid or methacrylic acid that carry at least one aromatic ring system (D11 ).
  • D1 cycloaliphatic (meth)acrylates
  • D2 Metal alkanoates
  • allyl compounds D4
  • vinyl ethers D5
  • N -vinyl lactams D6
  • At least one monomer (D), preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one monomer (D) can optionally be used.
  • cycloaliphatic (meth)acrylates (D1) are (meth)acrylates of alcohols which have at least one, preferably one or two and particularly preferably a cycloaliphatic ring system and have from 5 to 20 carbon atoms.
  • Preferred monomers are cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate and norbornyl (meth)acrylate; the respective acrylates are particularly preferred.
  • (Meth)acrylates of polyalkylene glycol monoalkyl ethers are preferably (meth)acrylic acid esters of mono-Ci-C4 alkyl ethers of poly-1,2-propylene glycol with a molecular weight between 134 and 1178 or polyethylene glycol with a molecular weight between 106 and 898, as well as ethyl englykol mono-Ci-C 4 alkyl ether or propylene glycol mono-Ci-C 4 alkyl ether.
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, 1,2-propanediol monomethyl ether, 1,2-propanediol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-n-butyl ether.
  • vinyl alkanoates preference is given to vinyl acetate, vinyl propionate, vinyl butanoate, vinyl pentanoate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl ester of neodecanoic acid (“Veova”), vinyl decanoate, vinyl dodecanoate, vinyl tridecanoate, vinyl isotridecanoate, vinyl tetradecanoate, vinyl pentadecanoate, vinyl hexadecanoate and vinyl octadecanoate, particularly preferably vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2-ethylhexanoate, and vinyl esters of neodecanoic acid (“Veova”), very particularly preferably vinyl acetate.
  • allyl compounds (D4) are allyl alcohol, allyl alcohol-Ci-C 4 alkyl ethers and allyl alkanoates of such carboxylic acids as listed under (D3).
  • vinyl ethers (D5) are cyclohexyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-butyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether and octadecyl vinyl ether
  • N-Vinyl lactams (D6) are preferably N-vinyl caprolactam and N-vinylpyrrolidone.
  • N-vinylimidazole is preferred.
  • styrene and 1-methylstyrene are preferred, particularly preferably styrene.
  • acrylonitrile and methacrylonitrile are preferred; acrylonitrile is particularly preferred.
  • Phenoxyethyl acrylate is preferred among the esters of acrylic acid or methacrylic acid that carry at least one aromatic ring system (D11).
  • optionally usable monomers (D) preferred are (D1), (D3), (D5) and/or (D8), particularly preferred are (D1), (D3) and/or (D5), very particularly preferred are ( D1) and/or (D3).
  • the stoichiometry of the monomers (A), (B), optional (C) and optional (D) is chosen so that the monomers in polymerized form have a molar incorporation ratio of 1: 0.5 to 2.0: 0 to 2.0 : have 0 to 0.1.
  • component (C) is present in the copolymer.
  • the stoichiometry of the monomers (A), (B), (C) and optionally (D) is chosen so that the monomers in polymerized form have a molar incorporation ratio of (A): (B): (C): (C): (D) from 1: 0.5 to 2.0: more than 0 to 1.0: 0 to 0.1, preferably from 1: 0.5 to 2.0: more than 0 to 0.5: 0 to 0.05, particularly preferably from 1:0.5 to 2.0:0.05 to 0.45:0.
  • the molar incorporation ratio (A): (B): (C): (D) is very particularly preferably from 1: 0.7 to 1.0: 0.1 to 0.4: 0.
  • no component (C) is present in the copolymer, most preferably no component (C) and no component (D).
  • the molar installation ratio (A): (B): (C): (D) is 1: 0.7 to 1.0: 0: 0.
  • the copolymer is obtainable in a first step by polymerizing a mixture of the monomers (A), (B), optionally (C) and optionally (D).
  • copolymers are obtainable by the usual copolymerization processes such as solvent polymerization, emulsion polymerization, precipitation polymerization or bulk polymerization, preferably solvent polymerization or bulk polymerization; they are preferably obtained via the said copolymerization processes.
  • the monomer components can be polymerized in bulk, in emulsion or, preferably, in solution. You can use a single monomer species or a mixture of several such monomer species for the monomer components.
  • the polymerization reaction is usually carried out at normal pressure and under a protective gas, such as nitrogen, but can also be carried out at elevated pressures of up to 25 bar, for example in an autoclave.
  • the polymerization temperatures are generally 50 to 250°C, in particular 90 to 210°C, especially 120 to 180°C, typically 140 to 160°C.
  • all conventional continuously or discontinuously operated apparatus such as stirred tanks, stirred tank cascades, tubular reactors or loop reactors, are suitable as polymerization reactors.
  • the polymerization is usually started by initiators that decompose radically; air or oxygen or organic peroxides and/or hydroperoxides as well as organic azo compounds are suitable for this purpose.
  • Suitable organic peroxides or hydroperoxides include, for example, diisopropylbenzene hydroperoxide, cumene hydroperoxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide and tert-butyl perisononate.
  • Azobisisobutyronitrile (“AIBN”) is suitable as an organic azo compound.
  • suitable regulators such as thioalcohols, aldehydes or ketones can be used during the polymerization.
  • solvents or emulsions are used in the polymerization
  • the usual high-boiling inert liquids such as aliphatic hydrocarbons, e.g. heptane, Shellsol® D70, white oil, lamp oil), aromatic hydrocarbons, e.g. Ethylbenzene, diethylbenzenes, toluene, xylenes or corresponding technical hydrocarbon mixtures such as Shellsol®, Solvesso® or Solvent Naphtha, are also considered, as well as dialkyl 1,2-cyclohexanedicarboxylate, preferably diisononyl 1,2-cyclohexanedicarboxylate.
  • the copolymer obtainable in this way preferably the copolymer obtained in this way, is reacted with the dialkylamine (E).
  • the reaction can take place at temperatures of 50 to 160 ° C, preferably 60 to 140 and particularly preferably 70 to 120 ° C.
  • the reaction can preferably take place in an inert solvent; the solvents listed above for the polymerization are preferred.
  • the dialkylamine (E) is at least one, preferably one or two and particularly preferably exactly one dialkylamine (E), the alkyl radicals of which are independently from one another at least 17 to 30, preferably 17 to 26, particularly preferably 17 to 24 and very particularly preferably 17 to 22 carbon atoms have alkyl radicals.
  • the two alkyl radicals can be the same or different, preferably the same.
  • the alkyl radicals having 17 to 30 carbon atoms can be linear or branched, preferably linear, with particular preference being n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, lignoceryl , ceryl and myricyl, and particularly particularly preferably n-octadecyl, n-nonadecyl and n-eicosyl.
  • Preferred dialkylamines (E) are di-n-octadecylamine, di-n-nonadecylamine and di-n-eicosylamine.
  • the sum of the statistical average of the number of carbon atoms in the monomer (B) and the statistical average of the number of carbon atoms of the alkyl radicals in the dialkylamine (E) is preferably at least 30, preferably at least 30.5 and particularly preferably at least 31.
  • Very particularly preferred in this embodiment are the combinations of 1-dodecene as monomer (B) with di-n-octadecylamine as dialkylamine (E), 1-undecene with di-n-nonadecylamine, 1-decene with di-n- eicosylamine, 1-undecene with di-n-octadecylamine, 1-dodecene with di-n-octadecylamine, 1-tridecene with di-n-octadecylamine and 1-tetradecene with di-n-octadecylamine.
  • the molar ratio of dialkylamine (E) based on incorporated units of dicarboxylic acid (A) in the copolymer is preferably at least 1.1:1, particularly preferably 1.2 to 2.0:1, very particularly preferably 1.3 to 1.8 : 1 and in particular 1.3 to 1.7: 1.
  • the molar ratio of dialkylamine (E) based on incorporated units of dicarboxylic acid (A) in the copolymer is preferably 1.1: 1 to 1.9 : 1, particularly preferably from 1.2: 1 to 1.8: 1 and very particularly preferably from 1.3: 1 to 1.7: 1.
  • dialkylamine is used in such a way that ideally one equivalent of dialkylamine (E) reacts with the built-in units of the dicarboxylic acid (A) in the copolymer to form amide groups and another equivalent of dialkylamine (E) neutralizes the free carboxyl groups formed.
  • the second reaction stage can be dispensed with if the monomer (A) is already used as a diamide or monoamide, preferably as a monoamide of the unsaturated dicarboxylic acid with dialkylamines (E).
  • the copolymer (II) after reaction with component (E) preferably has a weight-average molecular weight (M w ) in the range from 2000 to 20,000, particularly preferably from 2200 to 10,000 and very particularly preferably from 2500 to 8000 and in particular 2500 to 6000 g/mol (each determined by gel permeation chromatography against polystyrene as a standard).
  • M w weight-average molecular weight
  • the polydispersity is preferably up to 5, particularly preferably 2 to 5, very particularly preferably 2 to 4 and in particular 2 to 3.
  • copolymer (II) is used in fuels in the function of a paraffin dispersant ("WASA") and works particularly well together with copolymer (I) as a cold flow improver.
  • WASA paraffin dispersant
  • the dosage of the copolymers (I) and (II) in the middle distillate fuels according to the invention is as follows:
  • Copolymer (I) as a cold flow improver 10 to 2000 ppm by weight, preferably from 50 to 1000 ppm by weight, in particular from 75 to 750 ppm by weight and especially from 100 to 700 ppm by weight, copolymer (II) 10 to 5000 ppm by weight, preferably 25 to 3000 ppm by weight, in particular 50 to 2000 ppm by weight and especially 100 to 1000 ppm by weight and additionally optionally further additives selected from the group consisting of cold flow improvers, paraffin dispersants, Conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoam agents, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes and fragrances.
  • the mixtures according to the invention can be added to middle distillate fuels that are entirely of fossil origin, i.e. obtained from petroleum, as well as to fuels that contain a portion of biodiesel in addition to the petroleum-based portion, in order to improve their properties.
  • middle distillate fuels that are entirely of fossil origin, i.e. obtained from petroleum
  • fuels that contain a portion of biodiesel in addition to the petroleum-based portion, in order to improve their properties.
  • a significant improvement in the cold flow behavior of the middle distillate fuel ie a reduction in the CP values and/or CFPP values, is observed, regardless of the origin or composition of the fuel.
  • the separated paraffin crystals are effectively kept in suspension so that filters and pipes do not become blocked by sedimented paraffin.
  • the mixtures according to the invention have a good broad effect and thus ensure that the precipitated paraffin crystals are very well dispersed in a wide variety of middle distillate fuels.
  • the present invention also relates to fuels, in particular those with a biodiesel content, which contain the mixtures according to the invention.
  • the fuels or fuel additive concentrates also contain flow improvers (as described above), other paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoam agents, demulsifiers, detergents, cetane number as additional additives in the usual amounts.
  • flow improvers as described above
  • other paraffin dispersants such as paraffins, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoam agents, demulsifiers, detergents, cetane number
  • Improvers, solvents or diluents, dyes or fragrances or mixtures thereof are familiar to those skilled in the art and therefore do not need to be explained further here.
  • fuel oils are to be understood as meaning middle distillate fuels of fossil, vegetable or animal origin, biofuel oils (“biodiesel”) and mixtures of such middle distillate fuels and biofuel oils.
  • Middle distillate fuels refer in particular to fuels that are obtained by distilling crude oil as the first process step and boil in the range from 120 to 450 ° C.
  • middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
  • Low-sulfur middle distillates are preferably used, i.e. those which contain less than 350 ppm sulfur, in particular less than 200 ppm sulfur, especially less than 50 ppm sulfur. In special cases they contain less than 10 ppm sulfur; these middle distillates are also referred to as "sulfur-free".
  • These are generally crude oil distillates that have been subjected to hydrogen refining and therefore contain only small proportions of polyaromatic and polar compounds. These are preferably middle distillates which have 90% distillation points below 370 ° C, in particular below 360 ° C and in special cases below 330 ° C.
  • middle distillates can also be obtained from heavier petroleum fractions that can no longer be distilled under atmospheric pressure.
  • middle distillates include: hydrocracking, thermal cracking, catalytic cracking, coker processes and/or visbreaking. Depending on how the process is carried out, these middle distillates are low in sulfur or sulfur-free or are subjected to hydrogen refining.
  • the middle distillates preferably have aromatic contents of less than 28% by weight, in particular less than 20% by weight.
  • the normal paraffin content is between 5% and 50% by weight, preferably between 10 and 35% by weight.
  • middle distillate fuels are also to be understood as those fuels which can either be derived indirectly from fossil sources such as crude oil or natural gas or are produced from biomass via gasification and subsequent hydrogenation.
  • a typical example of a middle distillate fuel derived indirectly from fossil sources is the GTL ("gas-to-liquid") diesel fuel produced using Fischer-Tropsch synthesis.
  • GTL gas-to-liquid
  • a middle distillate is produced from biomass via the BTLf'biomass-to-liquid" process, which can be used either alone or in a mixture with other middle distillates as fuel.
  • the middle distillates also include hydrocarbons that are produced by hydrogenation Fats and fatty oils are obtained. They predominantly contain n-paraffins.
  • a further object of the present invention is the use of the mixture according to the invention to improve the cold flow properties of fuel oils and to improve the filterability of fuel oils containing cold flow improver additives.
  • the mixture according to the invention can also be used in biofuel oils and in mixtures of the middle distillates mentioned with biofuel oils to improve the cold flow behavior.
  • biofuel oils are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, in particular 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
  • Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids derived from vegetable and/or animal oils and/or fats.
  • Alkyl esters are preferably understood to mean lower alkyl esters, in particular C1 to C4 alkyl esters, which are produced by transesterification of the glycerides, in particular triglycerides, occurring in vegetable and/or animal oils and/or fats using lower alcohols, for example ethanol or especially methanol (“FAME”), are available.
  • Typical low alkyl esters based on vegetable and/or animal oils and/or fats that are used as biofuel oil or components for this are, for example, HVO (hydrogenated vegetable table oil), sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”) and especially rapeseed oil methyl ester (“RME”).
  • HVO hydrogenated vegetable table oil
  • PME palm oil methyl ester
  • SME soybean oil methyl ester
  • RME rapeseed oil methyl ester
  • the mixture according to the invention reduces the crystallization of paraffin crystals in fuels, especially those containing biofuel oils.
  • the content of ethylene, VAc and EHA in the polymers obtained was determined by NMR spectroscopy.
  • the viscosities were determined according to Ubbelohde DIN 51562.
  • copolymers were each used as a 60% by weight solution in Solvesso 150; the amounts given in the tables below refer to the 60% solution.
  • the cloud point (CP) of the additive fuel samples was determined according to ISO 3015 and the CFPP according to EN 116. To determine the delta CP value, the additive fuel samples in 500 ml glass cylinders were cooled to -16°C in a cold bath and stored at this temperature for 16 hours. The CP of each sample was determined in accordance with ISO 3015 from the 20 vol% soil phase separated at -16°C. The smaller the deviation of the CP of the 20 vol.% bottom phase from the original CP (Delta CP) of the respective fuel sample, the better the paraffins are dispersed.
  • the copolymers according to the invention significantly improve the cold flow behavior with regard to CFPP.
  • the fuels were mixed with the specified additives (ppm by weight) and the CFPP value was measured:

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Abstract

La présente invention porte sur une composition à partir de copolymères pour réduire la cristallisation de cristaux de paraffine dans des combustibles et/ou pour améliorer les propriétés d'écoulement à froid de mazouts et/ou pour améliorer la filtrabilité de mazouts contenus, et sur des mazouts qui contiennent une telle composition.
PCT/EP2023/071774 2022-08-16 2023-08-07 Composition pour réduire la cristallisation de cristaux de paraffine dans des combustibles WO2024037904A1 (fr)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320766A2 (fr) * 1987-12-16 1989-06-21 Hoechst Aktiengesellschaft Mélanges de polymères modifiant la viscosité de fractions de pétrole
EP0436151A1 (fr) * 1989-12-16 1991-07-10 BASF Aktiengesellschaft Distillat moyen de pétrole stable au froid contenant des polymères comme dispersants de paraffine
WO1995007944A1 (fr) 1993-09-13 1995-03-23 Basf Aktiengesellschaft Copolymeres et leurs produits de reaction avec des amines utiles comme additifs de carburants et de lubrifiants
WO1999025668A1 (fr) 1997-11-14 1999-05-27 Basf Aktiengesellschaft Procede de production d'octenes et de dodecenes essentiellement non ramifies par oligomerisation de butenes non ramifies
DE10227995A1 (de) 2002-03-15 2003-09-25 Oxeno Olefinchemie Gmbh Verfahren zur Hydroformylierung von Olefinen
DE10241266A1 (de) 2002-09-06 2004-03-18 Oxeno Olefinchemie Gmbh Verfahren zur Hydroformylierung von Olefinen
EP1433836A1 (fr) 2002-12-23 2004-06-30 Clariant GmbH Huiles combustibles à propriétés au froid améliorées.
EP1526167A2 (fr) 2003-10-25 2005-04-27 Clariant GmbH Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale
WO2005054314A2 (fr) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
EP1857529A1 (fr) 2006-05-16 2007-11-21 Clariant International Ltd. Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale
WO2009124979A1 (fr) 2008-04-10 2009-10-15 Basf Se Mélange d'alcools en c17
WO2016083130A1 (fr) 2014-11-27 2016-06-02 Basf Se Copolymère et son utilisation pour réduire la copolymérisation de cristaux de paraffine dans des carburants
WO2017202642A1 (fr) 2016-05-24 2017-11-30 Basf Se Copolymère et son utilisation pour la diminution de la cristallisation de cristaux de paraffine dans des carburants

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320766A2 (fr) * 1987-12-16 1989-06-21 Hoechst Aktiengesellschaft Mélanges de polymères modifiant la viscosité de fractions de pétrole
EP0436151A1 (fr) * 1989-12-16 1991-07-10 BASF Aktiengesellschaft Distillat moyen de pétrole stable au froid contenant des polymères comme dispersants de paraffine
WO1995007944A1 (fr) 1993-09-13 1995-03-23 Basf Aktiengesellschaft Copolymeres et leurs produits de reaction avec des amines utiles comme additifs de carburants et de lubrifiants
WO1999025668A1 (fr) 1997-11-14 1999-05-27 Basf Aktiengesellschaft Procede de production d'octenes et de dodecenes essentiellement non ramifies par oligomerisation de butenes non ramifies
DE10227995A1 (de) 2002-03-15 2003-09-25 Oxeno Olefinchemie Gmbh Verfahren zur Hydroformylierung von Olefinen
DE10241266A1 (de) 2002-09-06 2004-03-18 Oxeno Olefinchemie Gmbh Verfahren zur Hydroformylierung von Olefinen
EP1433836A1 (fr) 2002-12-23 2004-06-30 Clariant GmbH Huiles combustibles à propriétés au froid améliorées.
EP1526167A2 (fr) 2003-10-25 2005-04-27 Clariant GmbH Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale
WO2005054314A2 (fr) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
EP1857529A1 (fr) 2006-05-16 2007-11-21 Clariant International Ltd. Agent d'amélioration de l'écoulement à froid pour huiles combustibles d'origine végétale ou animale
WO2009124979A1 (fr) 2008-04-10 2009-10-15 Basf Se Mélange d'alcools en c17
WO2016083130A1 (fr) 2014-11-27 2016-06-02 Basf Se Copolymère et son utilisation pour réduire la copolymérisation de cristaux de paraffine dans des carburants
WO2017202642A1 (fr) 2016-05-24 2017-11-30 Basf Se Copolymère et son utilisation pour la diminution de la cristallisation de cristaux de paraffine dans des carburants

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