WO2024115211A1 - Homopolymères et copolymères d'éthers vinyliques pour réduire la cristallisation de cristaux de paraffine dans des carburants - Google Patents

Homopolymères et copolymères d'éthers vinyliques pour réduire la cristallisation de cristaux de paraffine dans des carburants Download PDF

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WO2024115211A1
WO2024115211A1 PCT/EP2023/082634 EP2023082634W WO2024115211A1 WO 2024115211 A1 WO2024115211 A1 WO 2024115211A1 EP 2023082634 W EP2023082634 W EP 2023082634W WO 2024115211 A1 WO2024115211 A1 WO 2024115211A1
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vinyl
vinyl ether
use according
alkyl
acid
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PCT/EP2023/082634
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English (en)
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Uwe Rebholz
Ivette Garcia Castro
Aleksandra Martyna GAJDA
Jochen Mezger
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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
    • 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
    • C10L10/16—Pour-point depressants
    • 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
    • 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

Definitions

  • the present invention relates to the use of homo- and copolymers of vinyl ethers for reducing crystallization of paraffin crystals in fuels.
  • Middle distillate fuels of fossil origin especially gas oils, diesel oils or light heating oils, which are obtained from mineral oil, have different contents of paraffins according to the origin of the crude oil.
  • CP cloud point
  • the platelet-shaped n-paraffin crystals form a kind of "house of cards structure” and the middle distillate fuel ceases to flow even though its predominant portion is still liquid.
  • the precipitated n-paraffins in the temperature range between cloud point and pour point (“PP") considerably impair the flowability of the middle distillate fuels; the paraffins block filters and cause irregular or completely interrupted fuel supply to the combustion units. Similar disruptions occur in the case of light heating oils.
  • MDFIs middle distillate flow improvers
  • EVA ethylene-vinyl carboxylate copolymers
  • EVA ethylene-vinyl acetate copolymers
  • WO 04 035715 describes the use of homopolymers of vinyl ethers as cold flow improver in fuel oil compositions.
  • Middle distillate A explicitly disclosed therein has a content of n-paraffins of 21 %.
  • EP 360419 A1 discloses the use of polymers of hydrocarbyl vinyl ethers in distillate fuel oils, the hydrocarbyl group containing 1 to 17 carbon atoms. Explicitly disclosed are copolymers of alkyl vinyl ethers with maleic acid anhydride or fumaric acid esters. No information about the paraffin content of the distillate fuel oils is given.
  • polymers (I) comprising at least one vinyl ether (V) in polymerised form as pour point depressant in hydrocarbon mixtures with a content of n-paraffins up to 20 wt%, preferably up to 19, more preferably up to 18, and even more preferably up to 17 wt%.
  • Preferred vinyl ethers (V) are of formula
  • R 1 is an alkyl group comprising 10 to 30, preferably 12 to 26, more preferably 14 to 24, even more preferably 16 to 20, and especially 18 carbon atoms.
  • alkyl vinyl ethers with an alkyl group comprising less than 10 carbon atoms, e.g. 8, 6, 4, 3, 2 or even 1 carbon atom.
  • the alkyl groups may be linear or branched, preferably linear.
  • Vinyl ethers (V) are preferably selected from the group consisting of decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether and octadecyl vinyl ether, more preferably from the group consisting of dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether and octadecyl vinyl ether, even more preferably from the group consisting of hexadecyl vinyl ether and octadecyl vinyl ether.
  • Especially vinyl ether (V) is octadecyl vinyl ether.
  • the vinyl ethers are vinyl ethers bearing linear alkyl groups, hence, n-dodecyl vinyl ether, n-tetradecyl vinyl ether, n-hexadecyl vinyl ether and n-octadecyl vinyl ether are preferred.
  • vinyl ethers other than vinyl ethers are isopropyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-butyl vinyl ether, and octyl vinyl ether.
  • Polymers (I) are preferably selected from the group consisting of homopolymers (la), polymers (lb), and copolymers (Ic), preferably selected from the group consisting of homopolymers (la) and copolymers (Ic).
  • the polymers comprising at least one vinyl ether (V) in polymerised form may be homopolymers of essentially one vinyl ether (V). Further to vinyl ether (V) such homopolymers may comprise one or more initiators or starters in polymerised form. These homopolymers are referred to as polymers (la).
  • the polymers comprising at least one vinyl ether (V) in polymerised form may be polymers of at least one vinyl ether (V) and at least one further vinyl ether different from the first one, preferably of at least two different vinyl ethers (V). Further to the vinyl ethers such polymers may comprise one or more initiators or starters in polymerised form. Such polymers are referred to as polymers (lb). Such polymers (lb) comprise essentially vinyl ethers only but are no homopolymers (la). Further to the vinyl ethers such polymers may comprise one or more initiators or starters in polymerised form.
  • the polymers comprising at least one vinyl ether (V) in polymerised form may be copolymers of at least one vinyl ether (V) and at least one further comonomer in polymerised form which is not a vinyl ether. Further to the comonomers such copolymers may comprise one or more initiators or starters in polymerised form. These copolymers are referred to as polymers (Ic). Polymers (I) usually exhibit a number average molecular weight Mn of from 2000 to 20000, preferably from 3000 to 15000, and more preferably from 5000 to 10000.
  • the weight average molecular weight Mw is from 3000 to 30000, preferably from 4000 to 25000, and more preferably from 5000 to 20000.
  • Polymers (la) and (lb) are usually obtainable by cationic polymerisation, while polymers (Ic) are obtainable by radical polymerisation.
  • the polydispersity of polymers (la) and (lb) is usually from 1 to 2, while the polydispersity of polymers (Ic) is usually in the range of from 1.5 to 12, preferably 1.2 to 10, more preferably of from 1.5 to 8, and especially from 1.7 to 5.
  • Molecular weights and polydispersity are determined by gel permeation chromatography (GPC) with polystyrene as molecular weight standard.
  • V vinyl ether (V) copolymers (Ic)
  • V vinyl ether (V) copolymers (Ic)
  • the copolymers (Ic) comprise at least one vinyl ether (V) and at least one or more of the comonomers (A), (B), (C) and/or (D).
  • the copolymers (Ic) comprise at least one vinyl ether (V) and at least one further comonomers (A), (B), (C) and/or (D), wherein the further comonomers are either of group (A) or of group (B) or of group (C) or of group (D), more preferably of group (B) or of group (C).
  • the copolymers (Ic) comprise exactly one vinyl ether (V) and exactly one further comonomer (A), (B), (C) and/or (D), wherein the further comonomer is either of group (A) or of group (B) or of group (C) or of group (D), more preferably of group (B) or of group (C).
  • the copolymers (Ic) comprise at least one vinyl ether (V) and at least two further comonomers (A), (B), (C) and/or (D), wherein the further comonomers are of different groups (A), (B), (C), and (D), more preferably of groups (A) and (C) or of groups (B) and (C).
  • Monomer (A) comprises at least one, preferably one to three, more preferably one or two and most preferably exactly one unsaturated dicarboxylic acid(s) or derivatives thereof.
  • - mono- or dialkyl esters preferably mono- or di-Ci-C4-alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters,
  • mixed esters preferably mixed esters having different Ci-C4-alkyl components, more preferably mixed methyl ethyl esters, and
  • the derivatives are preferably anhydrides in monomeric form or di-Ci-C4-alkyl esters, more preferably anhydrides in monomeric form.
  • Ci-C4-alkyl is understood to mean methyl, ethyl, /so-propyl, n- propyl, n-butyl, /so-butyl, sec-butyl and tert-butyl, preferably methyl and ethyl, more preferably methyl.
  • the unsaturated dicarboxylic acid comprises those dicarboxylic acids or derivatives thereof in which the two carboxyl groups are conjugated to 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 more preferably maleic acid, and derivatives thereof.
  • Monomer (A) is especially maleic anhydride.
  • Monomer (B) comprises at least one, preferably one to four, more preferably one to three, even more preferably one or two and especially exactly one a-olefin(s) having from at least 6 up to and including 30 carbon atoms.
  • the a-olefins (B) preferably have at least 8, more preferably at least 10, carbon atoms.
  • the a-olefins (B) preferably have up to and including 30, more preferably up to and including 22 and most preferably up to and including 16 carbon atoms.
  • monomer (B) is a mixture of different olefins
  • the determination of the number of carbon atoms should be based on the statistical average of the numbers of carbon atoms in the olefins present in the mixture. Accordingly, a mixture of 50 mol% of C22 olefin and 50 mol% of C16 olefin has a statistical average of 19 carbon atoms.
  • a-olefins present in the mixture have the above-specified number of carbon atoms, preferably at least 90 mol%, more preferably at least 95 mol% and most preferably at least 98 mol%.
  • the a-olefins may preferably be linear or branched, preferably linear, 1 -alkenes.
  • Examples thereof are 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 preference is given to 1 -decene, 1 -d
  • Monomer (C) is at least one, preferably one to four, more preferably one to three, even more preferably one or two and especially exactly one C4- to C22-alkyl ester(s) of acrylic acid or methacrylic acid, preferably of acrylic acid, or a mixture of such alkyl esters.
  • the alkyl radical in each case may be straight-chain or branched.
  • Suitable C4- to C22-alkyl esters of acrylic acid or methacrylic acid, preferably of acrylic acid, for component (C) are preferably the esters of acrylic acid and methacrylic acid with C4- to C18- alkanols, preferably with C4- to Cis-alkanols, more preferably with Cs- to Ci6-alkanols, even more preferably C10- to Ci4-alkanols and especially Ci2-alkanols, for example with n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, tert-pentanol, n-hexanol, n-heptanol, n- octanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, 2-propylheptanol, n-und
  • the alkanols are branched C13- or Cn-alkanols or mixtures thereof having a mean degree of branching according to the iso index of 1.2 to 3.0, especially of 1.7 to 2.5.
  • Alkanols of this kind or mixtures thereof are obtainable by oligomerization of C4 hydrocarbon streams, especially homogeneously or heterogeneously catalyzed oligomerization of technical grade C4 streams composed of 10% to 90% by weight of butane, 10% to 90% by weight of linear butenes (butene-1 , cis- and trans-butene-2) and 1% to 5% by weight of isobutene, for example of raffinate II.
  • a heterogeneous catalyst typical for this purpose comprises nickel.
  • the oligomerization is usually conducted at temperatures of 30 to 280°C and pressures of 10 to 300 bar. Oligomerization reactions of this kind are described, for example, in WO 99/25668.
  • the oligomerization products are subsequently hydroformylated and hydrogenated and thus give rise to 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 stearyl (meth)acrylate, more preferably n-dodecyl (meth)acrylate, n-tetradecyl (meth)acrylate or stearyl (meth)acrylate or mixtures thereof and most preferably the respective acrylates.
  • the weight ratio of monomers (C) is preferably at least 60 wt%.
  • the weight ratio of monomer (V) is at least 10 wt%, preferably in the range of from 10 to 30 wt%.
  • Further monomers (D), which are different than 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), N- vinyllactams (D6), N-vinylimidazoles (D7), ethylenically unsaturated aromatics (D8), sulfur dioxide (D9) and ethylenically unsaturated nitriles (D10).
  • cycloaliphatic (meth)acrylates (D1) (meth)acrylates of polyalkylene glycol monoalkyl ethers (D2), vinyl alkanoates (D3), allyl compounds (D4), N- vinyllactams (D6), N-vinylimidazoles (D7), ethylenically unsaturated aromatics (D8), sulfur dioxide
  • vinyl alkanoates (D3) and ethylenically unsaturated aromatics (D8) are preferred, especially vinyl alkanoates (D3). It is possible here for at least one monomer (D), preferably one to four, more preferably one to three, even more preferably one or two and especially exactly one monomer(s) (D) to be used optionally.
  • cycloaliphatic (meth)acrylates (D1) are (meth)acrylates of alcohols having at least one, preferably one or two and more preferably one cycloaliphatic ring system(s) and having 5 to 20 carbon atoms.
  • Preferred monomers are cyclopentyl (meth)acrylate, cyclohexyl (meth) acrylate and norbornyl (meth)acrylate, particular preference being given to the respective acrylates.
  • (Meth)acrylates of polyalkylene glycol monoalkyl ethers are preferably (meth)acrylic esters of mono-Ci-C4-alkyl ethers of poly-1 , 2-propylene glycol having a molar mass between 134 and 1178 or polyethylene glycol having a molar mass between 106 and 898, and also ethylene glycol mono-Ci-C4-alkyl ethers or propylene glycol mono-Ci-C4-alkyl ethers.
  • 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, particular preference to vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2- ethylhexanoate, and vinyl ester of neodecanoic acid (“Veova”), very particular preference to vinyl acetate.
  • allyl compounds (D4) preference is given to allyl alcohol, allyl alcohol Ci-C4-alkyl ethers and allyl alkanoates of those carboxylic acids as listed under (D3).
  • N-Vinyllactams (D6) are preferably N-vinylcaprolactam and N-vinylpyrrolidone.
  • N-vinylimidazoles (D7) preference is given to N-vinylimidazole.
  • ethylenically unsaturated aromatics preference is given to styrene and 1- methylstyrene, particular preference to styrene.
  • ethylenically unsaturated nitriles preference is given to acrylonitrile and methacrylonitrile, particular preference to acrylonitrile.
  • Preferred copolymers (Ic) are polymers comprising
  • V vinyl ether
  • B a-olefin having from at least 6 up to and including 36 carbon atoms, preferably from 8 to 30, and more preferably from 10 to 24 carbon atoms,
  • V at least one vinyl ether (V) and at least one vinyl alkanoate (D3), preferably at least one vinyl ether (V) and vinyl acetate, and
  • V vinyl ether
  • D8 ethylenically unsaturated aromatics
  • the copolymers (Ic) comprise at least 10 mol% of at least one vinyl ether (V) in polymerised form and the rest of at least one monomer other that vinyl ethers (V), preferably at least 20 mol%, more preferably at least 30 mol%, even more preferably at least 50 mol%, and especially at least 65 mol%.
  • the average number of carbon atoms in the alkyl moiety of the alkyl vinyl ether (V), the alkyl moiety of the (meth)acrylic acid alkyl ester (C), the a-olefin (B), and the carboxylic acid moiety of the vinyl alkanoate (D3) multiplied by their molar content in the copolymer is at least 10, preferably at least 12, more preferably at least 14, and especially at least 16.
  • the upper limit of such average number of carbon atoms is usually 30, preferably 28, more preferably 26, even more preferably 24, and especially 22.
  • a-olefin (B) only the number of carbon atoms of the moiety not incorporated into the polymer is taken into account, i.e. the number of carbon atoms of the a-olefin less 2 (two) for the double bond.
  • the vinyl alkanoate (D3) only the number of carbon atoms of the alkyl group of the carboxylic acid moiety is taken into account, i.e. the number of carbon atoms of the alkanoate less 1 (one) for the carboxyl group.
  • the homopolymers, polymers or copolymers (I) are obtainable by the customary copolymerization processes, for example solvent polymerization, emulsion polymerization, precipitation polymerization or bulk polymerization, preferably solvent polymerization or bulk polymerization; they are preferably obtained via said copolymerization processes.
  • the monomer components can be polymerized neat, in emulsion or preferably in solution. It is possible here to use a single monomer species or a mixture of several such monomer species for each monomer component.
  • the polymerization reaction is generally conducted at standard pressure and under a protective gas, such as nitrogen, but it is also possible to work at elevated pressures of up to 25 bar, for example in an autoclave.
  • the polymerization temperatures are generally 50 to 250°C, especially 90 to 210°C, in particular 120 to 180°C, typically 140 to 160°C.
  • Suitable polymerization reactors are in principle all customary continuous or batchwise apparatuses, for example a stirred tank, stirred tank cascade, tubular reactor or loop reactor.
  • the copolymers of vinylethers (lb) and especially the hompolymers of vinylethers (la) are obtained by bulk polymerisation.
  • the thus obtained polymers may be dissolved in a suitable solvent, e.g. the solvents mentioned below.
  • copolymers (Ic) are in a preferred embodiment obtained by radical polymerisation, preferably in solution.
  • Suitable initiators for radical polymerisation are air or oxygen of organic peroxides and/or hydroperoxides, and also organic azo compounds.
  • organic peroxides or hydroperoxides include diisopropylbenzene hydroperoxide, cumene hydroperoxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide and tert-butyl perisononanoate.
  • An example of a suitable organic azo compound is azobisisobutyronitrile ("Al BN").
  • suitable chain transfer agents in the polymerization as well, such as thio alcohols, aldehydes or ketones.
  • Suitable initiators for cationic polymerisation are typically started by Lewis- or Bronsted acids.
  • Bronsted acids are preferably selected from the group consisting of organic sulfonic acids and sulfuric acid, preferably sulfonic acids, more preferably aliphatic or aromatic sulfonic acids, even more preferably Ci- to C4-alkyl sulfonic acids, especially methane sulfonic acid and ethane sulfonic acid.
  • aromatic sulfonic acids are optionally substituted Ce- to Ci2-aromatic sulfonic acids, such as benzene sulfonic acid, p-toluene sulfonic acid, and para- Ce- to C2o-alkyl benzene sulfonic acid.
  • Lewis acids are aluminium, iron, titanium, and boron halides, very preferably aluminium, titanium, and boron halides, more preferably aluminium and boron halides, and especially boron halides.
  • aluminium halides are aluminium trihalides, alkylaluminium halides, and dialkylaluminium halides with aluminium trihalides being preferred.
  • a suitable aluminium trihalide hereinafter referred to as AIX3, is especially aluminium trifluoride, aluminium trichloride or aluminium tribromide, preferably aluminium trichloride.
  • a useful alkylaluminium halide is especially a mono(Ci- to C4-alkyl)aluminium dihalide or a di(Ci- to C4-alkyl)aluminium monohalide, for example methylaluminium dichloride, ethylaluminium dichloride, iso-butylaluminium dichloride, dimethylaluminium chloride or diethylaluminium chloride, diiso-butylaluminium chloride, preferably ethylaluminium dichloride, iso-butylaluminium dichloride, diethylaluminium chloride or diiso-butylaluminium chloride and very preferably ethylaluminium dichloride and iso-butylaluminium dichloride.
  • FeX 3 Especially suitable iron trihalides, hereinafter referred to as FeX 3 , are iron trifluoride, iron trichloride or iron tribromide, preferably iron trichloride.
  • boron trihalides hereinafter referred to as BX3, are boron trifluoride, boron trichloride or boron tribromide, preferably boron trifluoride.
  • Titanium halides TiX4 are for example are titanium tetrafluoride, titanium tetrachloride or titanium tetrabromide, preferably titanium tetrachloride.
  • Such a Lewis base preferably comprises at least one nitrogen or oxygen atom with at least one lone electron pair, preferably at least one oxygen atom with at least one lone electron pair, more preferably the Lewis base is selected from the group consisting of organic compounds with at least one ether or ester function, especially preferably selected from the group consisting of ethers, preferably aliphatic or cycloaliphatic ethers, more preferably selected from the group consisting of di(Ci- to C4-alkyl) ethers, tetrahydrofurane, tetrahydropyrane, and dioxane, and especially selected from the group consisting of tetrahydrofurane, tetrahydropyrane, and dioxane.
  • the customary high-boiling inert liquids are useful for this purpose, 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, and also dialkyl 1 ,2-cyclohexanedicarboxylates, preferably diisononyl 1 ,2- cyclohexanedicarboxylate.
  • aliphatic hydrocarbons e.g. heptane, Shellsol® D70, white oil, lamp oil
  • aromatic hydrocarbons e.g. ethylbenzene, diethylbenzenes, toluene, xylenes or corresponding technical hydrocarbon mixtures
  • the polymers (I) according to the present invention usually are formulated and applied to the hydrocarbon mixtures together with at least one cold flow improver (II):
  • Component (II) is at least one cold flow improver which is selected from the group consisting of compounds (111) to (II6) listed below.
  • Suitable cold flow improvers are in principle all organic compounds which are capable of improving the flow performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. More particularly, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flow improvers, MDFIs) typically used in the case of middle distillates of fossil origin, i.e. in the case of customary mineral diesel fuels. However, it is also possible to use organic compounds which partly or predominantly have the properties of a wax antisettling additive ("WASA”) when used in customary diesel fuels. They can also act partly or predominantly as nucleators. It is also possible to use mixtures of organic compounds effective as MDFIs and/or effective as WASAs and/or effective as nucleators.
  • MDFIs middle distillate flow improvers
  • WASA wax antisettling additive
  • the cold flow improver is selected from:
  • Suitable C2- to C4o-olefin monomers for the copolymers of class (111) are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 carboncarbon double bonds, especially having one carbon-carbon double bond.
  • the carbon-carbon double bond may be arranged either terminally (a-olefins) or internally.
  • preference is given to a-olefins particular preference to a-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and in particular ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters and further olefins.
  • further olefins are also copolymerized, they are preferably higher in molecular weight than the abovementioned C2- to C4o-olefin base monomers.
  • the olefin base monomer used is ethylene or propene
  • suitable further olefins are especially C10- to C4o-a- olefins. Further olefins are in most cases only additionally copolymerized when monomers with carboxylic ester functions are also used.
  • Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with Ci- to C20- alkanols, especially Ci- to Cw-alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2- ethylhexanol, nonanol and decanol, and structural isomers thereof.
  • Suitable alkenyl carboxylates are, for example, C2- to Ci4-alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbyl radical may be linear or branched.
  • preference is given to the vinyl esters.
  • carboxylic acids with a branched hydrocarbyl radical preference is given to those whose branch is in the a position to the carboxyl group, and the a-carbon atom is more preferably tertiary, i.e. the carboxylic acid is what is called a neocarboxylic acid.
  • the hydrocarbyl radical of the carboxylic acid is preferably linear.
  • alkenyl carboxylates examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference being given to the vinyl esters.
  • a particularly preferred alkenyl carboxylate is vinyl acetate; typical copolymers of group (111) resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs"), which are some of the most frequently used.
  • Ethylene-vinyl acetate copolymers usable particularly advantageously and the preparation thereof are described in WO 99/29748.
  • Suitable copolymers of class (111) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group.
  • copolymers which, as well as the alkenyl carboxylate(s), comprise at least one olefin and/or at least one (meth)acrylic ester in copolymerized form.
  • Terpolymers of a C2- to C4o-a-olefin, a Ci- to C2o-alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2- to Ci4-alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (111).
  • Terpolymers of this kind are described in WO 2005/054314.
  • a typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate or 2-propylheptyl acrylate and vinyl acetate.
  • the at least one or the further ethylenically unsaturated monomer(s) are copolymerized in the copolymers of class (111) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer.
  • the main proportion in terms of weight of the monomer units in the copolymers of class (111) therefore originates generally from the C2- to C40 base olefins.
  • the copolymers of class (111) preferably have a number-average molecular weight Mn of 1000 to 20 000, more preferably of 1000 to 10 000 and especially of 1000 to 8000.
  • Typical comb polymers of component (II2) are, for example, obtainable by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an a-olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
  • Further suitable comb polymers are copolymers of a-olefins and esterified comonomers, for example esteri- fied copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
  • Suitable comb polymers may also be polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers.
  • Comb polymers suitable as components of class (II2) are, for example, also those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974). Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as components of class (113) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also in US 4 491 455. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000.
  • Polar nitrogen compounds suitable as components of class (II4) may be either ionic or nonionic and preferably have at least one substituent, especially at least two substituents, in the form of a tertiary nitrogen atom of the general formula >NR 7 in which R 7 is a Cs- to C4o-hydrocarbyl radical.
  • the nitrogen substituents may also be quaternized, i.e. be in cationic form.
  • nitrogen compounds examples are ammonium salts and/or amides which are obtainable by the reaction of at least one amine substituted by at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines preferably comprise at least one linear Cs- to C4o-alkyl radical.
  • Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures especially amine mixtures obtainable on the industrial scale, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann’s Encyclopedia of Industrial Chemistry, 6th Edition, "Amines, aliphatic” chapter.
  • Acids suitable for the reaction are, for example, cyclohexane-1 ,2-dicarboxylic acid, cyclohexene-1 ,2- dicarboxylic acid, cyclopentane-1 ,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acids substituted by long-chain hydrocarbyl radicals.
  • the component of class (II4) is an oil-soluble reaction product of poly(C2- to C2o-carboxylic acids) having at least one tertiary amino group with primary or secondary amines.
  • the poly(C2- to C2o-carboxylic acids) which have at least one tertiary amino group and form the basis of this reaction product comprise preferably at least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids have preferably 2 to 10 carbon atoms, and are especially acetic acid units.
  • the carboxylic acid units are suitably bonded to the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are bonded via hydrocarbon chains.
  • the component of class (II4) is preferably an oil-soluble reaction product based on poly(C2- to C2o-carboxylic acids) which have at least one tertiary amino group and are of the general formula (IVa) or IVb in which the variable A is a straight-chain or branched C2- to Ce-alkylene group or the moiety of the formula (V)
  • variable B is a Ci- to Ci9-alkylene group.
  • the compounds of the general formulae (IVa) and (IVb) especially have the properties of a WASA.
  • the preferred oil-soluble reaction product of component (114), especially that of the general formula (IVa) or IVb, is an amide, an amide-ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups have been converted to amide groups.
  • Straight-chain or branched C2- to Ce-alkylene groups of the variable A are, for example, 1 ,1- ethylene, 1 ,2-propylene, 1 ,3-propylene, 1 ,2-butylene, 1 ,3-butylene, 1 ,4-butylene, 2-methyl-1 ,3- propylene, 1 ,5-pentylene, 2-methyl-1 ,4-butylene, 2,2-dimethyl-1 ,3-propylene, 1 ,6-hexylene (hexamethylene) and especially 1 ,2-ethylene.
  • the variable A comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.
  • Ci- to Ci9-alkylene groups of the variable B are, for example, methylene, 1 ,2-ethylene, 1 ,3- propylene, 1 ,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene.
  • the variable B comprises preferably 1 to 10 and especially 1 to 4 carbon atoms.
  • the primary and secondary amines as a reaction partner for the polycarboxylic acids to form component (II4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines may be selected from a multitude of amines which bear hydrocarbyl radicals which may optionally be bonded to one another.
  • These parent amines of the oil-soluble reaction products of component (II4) are usually secondary amines and have the general formula HN(R 8 )2 in which the two variables R 8 are each inde- pendently straight-chain or branched Cw- to Cso-alkyl radicals, especially C14- to C24-alkyl radicals.
  • These relatively long-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals derive from naturally occurring fatty acids and from derivatives thereof.
  • the two R 8 radicals are preferably identical.
  • the secondary amines mentioned may be bonded to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; it is also possible for only a portion to be present as amide structures and another portion as ammonium salts. Preferably only few, if any, free acid groups are present.
  • the oil-soluble reaction products of component (II4) are preferably present completely in the form of the amide structures.
  • component of class (II4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acidcontaining polymers, as described in WO 93/18115.
  • polar nitrogen-containing compounds are copolymers of alphaolefins with maleic anhydride and optionally further comonomers which are further reacted with primary or secondary amines.
  • the polar nitrogen-containing compounds are copolymers of C10- to C20- alpha-olefins with maleic anhydride which are further reacted with primary or secondary Cs-Cw- alkyl amines which are bound via amide- and/or imide-groups.
  • Examples are disclosed in EP 1526167 A designated as component B), especially those in Table 4 thereof, or in EP 1857529 designated as component B) which are incorporated by reference.
  • copolymers are disclosed in WO 16/83130 which are incorporated by reference as copolymers of unsaturated dicarboxylic acids, Ce- to C2o-alpha olefins, Ce- to C20- alkylesters of acrylic acid or methacrylic acid, and optionally further copolymerizable monomers which are further reacted with dialkylamines bearing C17- to Cso-alkyl groups.
  • WO 16/83130 are incorporated by reference as copolymers of unsaturated dicarboxylic acids, Ce- to C2o-alpha olefins, Ce- to C20- alkylesters of acrylic acid or methacrylic acid, and optionally further copolymerizable monomers which are further reacted with dialkylamines bearing C17- to Cso-alkyl groups.
  • Examples 1 to 10 in Table A of WO 16/83130 are incorporated by reference as copolymers of unsaturated dicarboxylic acids, Ce- to C2
  • Further polar nitrogen-containing compounds are reaction products of phthalic anhydride with amines, especially dialkylamines, as described in US 4211534.
  • Sulfocarboxylic acids, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of the component of class (II5) are, for example, the oil-soluble carboxamides and carboxylic esters of ortho-sulfobenzoic acid, in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957.
  • Poly(meth)acrylic esters suitable as cold flow improvers of the component of class (II6) are either homo- or copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth)acrylic esters which differ with regard to the esterified alcohol.
  • the copolymer optionally comprises another different olefinically unsaturated monomer in copolymerized form.
  • the weight-average molecular weight of the polymer is preferably 50 000 to 500 000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C14- and Cis-alcohols, the acid groups having been neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic esters are described, for example, in WO 00/44857.
  • the inventive mixtures can preferably be used in fuels in their function as a paraffin dispersant ("WASA").
  • WASA paraffin dispersant
  • the inventive mixtures often display their action as a paraffin dispersant particularly well only once together with the flow improvers.
  • Copolymer (I) is added to the fuels so that the middle distillate fuels comprise the copolymer in an amount of typically 10 to 5000 ppm by weight, preferably of 20 to 3000 ppm by weight, especially of 30 to 2000 ppm by weight and in particular of 50 to 1000 ppm by weight.
  • the inventive middle distillate fuels comprise component (II), in addition to component (I), in an amount of typically 1 to 2000 ppm by weight, preferably of 5 to 1000 ppm by weight, especially of 10 to 750 ppm by weight and in particular of 50 to 500 ppm by weight, for example of 150 to 400 ppm by weight.
  • the polymer according to the invention are used for treating hydrocarbon mixtures in generals.
  • such hydrocarbon mixtures may be fuel oils.
  • Fuel oils shall be understood to mean 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 are especially understood to mean fuels which are obtained by distilling crude oil as the first process step and boil within the range from 120 to 450°C.
  • Such middle distillate fuels are used especially as diesel fuel, heating oil or kerosene, particular preference being given to diesel fuel and heating oil.
  • They are generally crude oil distillates which have been subjected to refining under hydrogenating conditions and therefore comprise only small proportions of polyaromatic and polar compounds. They are preferably those middle distillates which have 90% distillation points below 370°C, especially below 360°C and in special cases below 330°C.
  • Low-sulfur and sulfur-free middle distillates may also be obtained from relatively heavy mineral oil fractions which cannot be distilled under atmospheric pressure.
  • Typical conversion processes for preparing middle distillates from heavy crude oil fractions include: hydrocracking, thermal cracking, catalytic cracking, coking processes and/or visbreaking. Depending on the process, these middle distillates are obtained in low-sulfur or sulfur-free form, or are subjected to refining under hydrogenating conditions.
  • the middle distillates preferably have aromatics contents of below 28% by weight, especially below 20% by weight.
  • the content of normal paraffins is between 5% by weight and 50% by weight, preferably between 10 and 35% by weight.
  • middle distillate fuels shall also be understood here to mean those fuels which can either be derived indirectly from fossil sources such as mineral oil or natural gas, or else are produced from biomass via gasification and subsequent hydrogenation.
  • a typical example of a middle distillate fuel which is derived indirectly from fossil sources is the GTL ("gas-to-liquid”) diesel fuel obtained by means of Fischer-Tropsch synthesis.
  • a middle distillate is prepared from biomass, for example, via the BTL ("biomass-to-liquid”) process, and can be used as fuel either alone or in a mixture with other middle distillates.
  • the middle distillates also include hydrocarbons which are obtained by the hydrogenation of fats and fatty oils. They comprise predominantly n-paraffins.
  • the fuel is a diesel fuel (absent any additives) with a CP value according to ASTM D2500/ASTM D97 of 0 to -15 °C, preferably 0 to -10 °C, and more preferably -5 to -10 °C and/or, preferably and with a content of n-paraffines of from 10 to 27 % by weight, more preferably of from 15 to 25 % by weight, and most preferably from 17 to 23 % by weight.
  • a diesel fuel abent any additives
  • ASTM D2500/ASTM D97 of 0 to -15 °C, preferably 0 to -10 °C, and more preferably -5 to -10 °C and/or, preferably and with a content of n-paraffines of from 10 to 27 % by weight, more preferably of from 15 to 25 % by weight, and most preferably from 17 to 23 % by weight.
  • the inventive copolymer can also be used in biofuel oils and in mixtures of the middle distillates mentioned with biofuel oils, in order to improve cold flow characteristics.
  • Mixtures of this kind are commercially available and usually comprise the biofuel oils in minor amounts, typically in amounts of 1% to 30% by weight, especially of 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 which derive from vegetable and/or animal oils and/or fats.
  • Alkyl esters are preferably understood to mean lower alkyl esters, especially Ci- to C4-alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and/or animal oils and/or fats, especially triglycerides, by means of lower alcohols, for example ethanol or in particular methanol (“FAME").
  • Typical lower alkyl esters which are based on vegetable and/or animal oils and/or fats and find use as a biofuel oil or components thereof are, for example, HVO (hydrogenated vegetable oil), sunflower methyl ester, palm oil methyl ester (“PME”), soya oil methyl ester (“SME”) and especially rapeseed oil methyl ester ("RME”).
  • HVO hydrogenated vegetable oil
  • PME palm oil methyl ester
  • SME soya oil methyl ester
  • RME rapeseed oil methyl ester
  • the hydrocarbon mixtures to which the polymers (I) or their mixtures with at least one component (II) may be added are unconverted oils (UCO), also referred to as hydrocracker gasoils or slack waxes.
  • UAO unconverted oils
  • VGO vacuum gasoil
  • Such unconverted oils are usually used as a feedstock for steamcrackers or an FCC unit (fluid catalytic cracker).
  • Unconverted oils typically have a boiling range between 300 °C initial boiling point (IBP) and 525 °C final boiling point (FBP).
  • n-paraffins The content of n-paraffins is usually from 5 to 15, preferably from 7 to 13 %. Most of the n-paraffins comprise more than 19 carbon atoms, preferably 24 to 30, and more preferably 26 to 29 carbon atoms. The content of n-paraffins comprising up to 19 carbon atoms is less than 1 %.
  • compositions it is possible, through the use of the inventive compositions, to improve a number of properties of hydrocarbon mixtures and fuels. Mention shall be made here by way of example merely of the additional effect as a cloud point depressant (CPD) or as a booster together with a flow improver for further improvement of the CFPP.
  • CPD cloud point depressant
  • the inventive compositions can be added either to middle distillate fuels entirely of fossil origin, i.e. those that have been obtained from mineral oil, or to fuels which, as well as the proportion based on mineral oil, comprise a proportion of biodiesel, in order to improve the properties thereof.
  • a distinct improvement in the cold flow characteristics of the middle distillate fuel is observed, i.e. a lowering of the CP values and/or CFPP values, irrespective of the origin or the composition of the fuel.
  • the paraffin crystals which precipitate out are effectively kept suspended, and so there are no blockages of filters and lines by sedimented paraffin.
  • the inventive copolymers have a good activity spectrum and thus achieve very good dispersion of the paraffin crystals which precipitate out in a wide variety of different middle distillate fuels.
  • the fuels or fuel additive concentrates also comprise, as further additives in amounts customary therefor, flow improvers (as described above), further paraffin dispersants, conductiv- ity improvers, anticorrosion additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
  • flow improvers as described above
  • further paraffin dispersants as described above
  • conductiv- ity improvers anticorrosion additives
  • lubricity additives antioxidants
  • metal deactivators antifoams
  • demulsifiers demulsifiers
  • detergents cetane number improvers
  • solvents or diluents dyes or fragrances or mixtures thereof.
  • Pour Point was determined according to ISO 3019 using an PAC optipp analyzer.
  • Component 1 Homopolymer of n-octadecyl vinyl ether, obtained by BFs-catalysed bulk polymerisation. Melt viscosity 180 mPas at 120 °C, Mw ca. 28000 g/mol. 50 % solution in Solvesso 150.
  • Component 2 Copolymer of 30 wt% n-octadecyl vinyl ether and 70 wt% lauryl acrylate, obtained by radical solution polymerisation. Mn ca. 6500, Mw ca. 16900 g/mol, polydispersity 2.5 (determined via Size Exclusion Chromatography in THF, PLgel Mixed-B column, PMMA- Standard of Fa. PSS with molecular weight of from 800 to 1820000).

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Abstract

La présente invention concerne l'utilisation d'homopolymères et de copolymères d'éthers vinyliques pour réduire la cristallisation de cristaux de paraffine dans des carburants.
PCT/EP2023/082634 2022-11-30 2023-11-22 Homopolymères et copolymères d'éthers vinyliques pour réduire la cristallisation de cristaux de paraffine dans des carburants WO2024115211A1 (fr)

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US4211534A (en) 1978-05-25 1980-07-08 Exxon Research & Engineering Co. Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils
EP0061895A2 (fr) 1981-03-31 1982-10-06 Exxon Research And Engineering Company Additif pour améliorer l'écoulement des carburants distillés et leurs concentrats
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