[go: up one dir, main page]

EP0931824B1 - Procédés d'amélioration des propriétés d'écoulement à froid d'huiles combustibles - Google Patents

Procédés d'amélioration des propriétés d'écoulement à froid d'huiles combustibles Download PDF

Info

Publication number
EP0931824B1
EP0931824B1 EP98124678A EP98124678A EP0931824B1 EP 0931824 B1 EP0931824 B1 EP 0931824B1 EP 98124678 A EP98124678 A EP 98124678A EP 98124678 A EP98124678 A EP 98124678A EP 0931824 B1 EP0931824 B1 EP 0931824B1
Authority
EP
European Patent Office
Prior art keywords
mol
weight
copolymer
vinyl esters
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98124678A
Other languages
German (de)
English (en)
Other versions
EP0931824A2 (fr
EP0931824A3 (fr
Inventor
Matthias Dr. Krull
Werner Dr. Reimann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP0931824A2 publication Critical patent/EP0931824A2/fr
Publication of EP0931824A3 publication Critical patent/EP0931824A3/fr
Application granted granted Critical
Publication of EP0931824B1 publication Critical patent/EP0931824B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic

Definitions

  • the present invention relates to a method for improving the Cold flow properties of mineral oils and mineral oil distillates, while simultaneously the filterability of the oils is maintained, an additive for improving the Cold flow properties and fuel oils containing the additives.
  • Crude oils and middle distillates obtained by the distillation of crude oils such as gas oil, Diesel oil or fuel oil
  • Crude oils and middle distillates obtained by the distillation of crude oils contain different depending on the origin of the crude oils
  • Amounts of n-paraffins the platelet-shaped when the temperature is lowered Crystals crystallize and partially agglomerate with the inclusion of oil. This leads to a deterioration of the flow properties of these oils Distillates, whereby, for example, in extraction, transport, storage and / or use of mineral oils and mineral oil distillates may occur.
  • this crystallization phenomenon can occur during transport Pipelines, especially in winter to deposits on the pipe walls, in Individual cases, e.g. at standstill of a pipeline, even to its complete blockage to lead.
  • the flow and cold behavior of mineral oils and mineral oil distillates is through Specification of the cloud point (determined according to ISO 3015), the pour point (determined according to ISO 3016) and the Cold Filter Plugging Point (CFPP, determined according to EN 116) described. These parameters are measured in ° C.
  • Typical flow improvers for crude oils and middle distillates are copolymers of Ethylenes with carboxylic acid esters of vinyl alcohol. How to set after the DE-A-11 4 799 petroleum distillate fuels having a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate having a molecular weight of between about 1,000 and 3,000. Preference is given to copolymers which contain about 60 to 99 wt .-% of ethylene and about 1 to 40 wt .-% vinyl acetate. They are especially effective when they pass through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2100 atm were made (DE-A-19 14 756).
  • EP-A-0 493 769 discloses terpolymers consisting of ethylene, vinyl acetate and neononane or vinyl neodecanoate, and their use as Additives for mineral oil distillates.
  • DE-A-22 06 719 discloses mixtures of ethylene-vinyl acetate copolymers with different Comonomerwitz to improve the cold flow behavior of middle distillates.
  • DE-A-20 37 673 discloses synergistic mixtures of ethylene-vinyl ester copolymers different molecular weights as flow improvers.
  • EP-A-0 254 284 discloses blends of ethylene / vinyl acetate copolymers with Ethylene / vinyl acetate / diisobutylene terpolymers as flow improvers for mineral oils and mineral oil distillates.
  • EP-A-0 648 257 discloses blends of at least 2 ethylene / vinyl ester copolymers, where the vinyl esters of carboxylic acids with 2 to 7 Derive carbon atoms.
  • EP-B-0 648 258 discloses ternary mixtures of ethylene / vinyl ester copolymers, wherein one of the blend components is between 7.5 and 35 and% of the vinyl ester comonomer and another of the mixture components below 10 mol% of Contains vinyl ester comonomers.
  • EP-A-0 113 581 discloses blends of two ethylene / vinyl ester copolymers, in the vinyl esters derived from carboxylic acids of 1 to 4 carbon atoms is.
  • One of the copolymers is a paraffin crystal nucleating agent, while the other Copolymer is a growth inhibitor.
  • EP-A-0 741 181 discloses blends of two copolymers, one of which at least one vinyl ester having alkyl or alkenyl radicals with more than 4 Contains carbon atoms as comonomers.
  • EP-A-0 648 256 discloses ethylene-vinyl ester copolymers as cold flow improvers for mineral oils.
  • the vinyl esters carry acid residues of C 1 to C 28 , and their molar content of the copolymer is less than 11%.
  • WO-96/34073 discloses an additive as a cold flow improver for mineral oils, 10 ° C under Cloud Point have a wax content of less than 2 wt .-%.
  • the Additive comprises a copolymer of ethylene and an unsaturated vinyl ester except Vinyl acetate, wherein the molar ratio of the vinyl ester is greater than 10%.
  • EP-A-0 649 456 discloses copolymers of ethylene and esters of unsaturated Alcohols with which the cold flow behavior of oils with a wax content of more than 2.5 wt .-% can be improved.
  • EP-A-0 706 306 discloses additives for stabilizing CFPP in middle distillates. These additives contain mixtures of copolymers and terpolymers of ethylene and Vinylestern. A disadvantage of the mixtures proposed there is the proportion of highly crystalline polymer fractions, especially at low oil and / or Additive temperatures during additivation The filterability of the additized oils above the cloud point.
  • the data in% by weight relate to the total weight of the mixture of A) and B).
  • Another object of the invention is a fuel oil, which defined above Composition of A and B contains.
  • the mixture of the copolymers from 20 to 40 wt .-% of Components A) and 60 to 80 wt .-% of component B).
  • Preferred vinyl esters for component B) are vinyl acetate, vinyl propionate, Vinylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, here in particular of neononan, neodecane and neoundecanoic acid.
  • Preferred acrylic acid esters are acrylic acid alkyl esters with alcohol radicals from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as methyl acrylate, Ethyl acrylate and 2-ethylhexyl acrylate.
  • R 1 and R 2 are preferably hydrogen.
  • R 3 preferably denotes a neoalkyl radical having 7 to 11 carbon atoms, in particular a neoalkyl radical having 8, 9 or 10 carbon atoms.
  • the neoalkyl acids from which the abovementioned neoalkyl radicals can be derived are described by the formula 4:
  • the vinyl ester used for the copolymerization therefore has the formula 5:
  • Copolymer A) preferably contains 5 to 10 mol%, in particular 7 to 10 mol% of the structural units of the formula 2.
  • Copolymer B) is preferably an ethylene copolymer with a Comonomer content of 10 to 20 mol%, preferably 13 to 18 mol%.
  • suitable Comonomers are vinyl esters of aliphatic carboxylic acids having 2 to 15 carbon atoms, see above in that B) in particular an ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, Ethylene-vinyl acetate-neononanoic acid vinyl ester copolymer or a Ethylene-vinyl acetate-neodecanoic acid vinyl ester terpolymer.
  • Comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Particularly preferred are ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers.
  • the copolymers used in the invention are by the usual Copolymerization processes such as suspension polymerization, Solution polymerization, gas phase polymerization or High pressure mass polymerization can be produced.
  • Preferred is the High-pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350 ° C, in particular 100 to 250 ° C.
  • the reaction of the monomers is by radicals forming initiators (radical chain starter) initiated.
  • radicals forming initiators radical chain starter
  • Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, Dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are individually or as a mixture of two or more substances in amounts of from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
  • components A and B have melt viscosities at 140 ° C of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
  • component A has a higher by at least 100 mPas Melt viscosity as component B.
  • the desired melt viscosity of Blends are made by selecting the individual components and varying the Blend ratio of the copolymers set.
  • copolymers mentioned under A) and B) may contain up to 5% by weight of further comonomers.
  • Such comonomers may be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C 1 to C 20 alkyl radicals, isobutylene and higher olefins having at least 5 carbon atoms.
  • Preferred higher olefins are hexene, isobutylene, 4-methylpentene, octene and / or diisobutylene.
  • High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene may be included in the reaction mixture.
  • the solvent-free operation is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and above supplied to one or more side branches.
  • the monomer streams be composed differently (EP-A-0 271 738).
  • the mixtures of components A and B are mineral oils or Mineral oil distillates added in the form of solutions or dispersions. These Solutions or dispersions preferably contain 1 to 90, in particular 5 to 80% by weight of the mixtures.
  • Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, Toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvent Naphtha, ®Shellsoll AB, ® Solvesso 150, ® Solvesso 200, ®Exxsol-, ®ISOPAR- and ®Shellsol D types.
  • the specified solvent mixtures contain different amounts of aliphatic and / or aromatic Hydrocarbons.
  • the aliphatics can be straight chain (n-paraffins) or branched his (iso-paraffins).
  • Aromatic hydrocarbons can mono-, di- or be polycyclic and optionally carry one or more substituents.
  • the Mixtures also together with one or more oil-soluble co-additives already used by itself the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
  • oil-soluble co-additives are polar Compounds which cause a paraffin dispersion (paraffin dispersants), as well as comb polymers.
  • Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed.
  • paraffin dispersants have become oil-soluble polar compounds having ionic or polar groups, e.g. amine salts and / or amides obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (U.S. 4,211,534).
  • paraffin dispersants are copolymers of the Maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are reacted can (EP-A-0 154 177), the reaction products of Alkenylspirobislactonen with Amines (EP-A-0 413 279) and according to EP-A-0 606 055 reaction products of Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkenyl ether of lower unsaturated Alcohols.
  • Alkylphenol-formaldehyde resins are also known as paraffin dispersants suitable.
  • Comb polymers are polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30% of the monomers have side chains (compare Comb-like Polymers - Structure and Properties, NA Platé and VP Shibaev, J. Polym, Sci Macromolecular Revs 1974, 8, 117 ff).
  • Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf., EP-A-0 153 176), copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide (cf. A-0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • fumarate / vinyl acetate copolymers cf., EP-A-0 153 176
  • copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide cf. A-0 320 766
  • further esterified olefin / maleic anhydride copolymers polymers and cop
  • the mixing ratio (in parts by weight) of the mixtures according to the invention with paraffin dispersants and / or comb polymers is in each case from 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • middle distillates are particularly well suited.
  • Middle distillates are referred to in particular those mineral oils by Crude oil distillation and boiling in the range of 120 to 400 ° C, such as kerosene, jet fuel, diesel and heating oil.
  • the invention Fuels preferably contain less than 350 ppm and especially less than 200 ppm sulfur.
  • Their content of n-paraffins, the chain lengths, determined with GC of 18 carbon atoms or more, is at least 8 area%, preferably at more than 10 area%.
  • EP-A-0 796 306 Compared to the nearest state of the Technology, in particular to EP-A-0 796 306, has the advantage of inventive method in an improved solubility of the additives, so that the filterability of the oils additivated with them even at low Blending temperatures of oil and / or additive is maintained. Furthermore the mixtures of the invention show pronounced synergistic effects compared to the individual components in CFPP subsidence.
  • the mixtures according to the invention can be used alone or together with other additives are used, for example with Dewaxing aids, corrosion inhibitors, antioxidants, lubricity additives, Dehazem, conductivity improver, cetane improver or Sludge inhibitors.
  • the determination of the boiling characteristics is carried out in accordance with ASTM D-86, the determination of the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
  • the paraffin content is determined by gas chromatographic separation of the oil (detection by FiD) and calculation of the integral of the n paraffins ⁇ C 18 in relation to the total integral. As an approximation, this area integral of n-paraffins ⁇ C 18 is equated with wt% n-paraffins ⁇ C 18 in relation to the total integral.
  • Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Test oil 6 Initial boiling point 180 ° C 169 ° C 183 ° C 183 ° C 184 ° C 182 ° C 20% 267 ° C 255 ° C 226 ° C 232 ° C 258 ° C 243 ° C 90% 350 ° C 350 ° C 330 ° C 358 ° C 329 ° C 351 ° C 95% 365 ° C 364 ° C 347 ° C 378 ° C 344 ° C 366 ° C Cloud point -0.4 ° C -1 ° C -9 ° C + 4 ° C -5 ° C -3 ° C CFPP -3 ° C -3 ° C -12 -4 ° C -9 ° C -6 ° C (90-20)% 83 ° C 95 ° C 104 ° C 126 ° C 71 ° C 108 ° C n-paraffins ⁇ C 18 /
  • the CFPP value of the oil additized with the specified amount of flow improver was measured immediately after the additization and the remainder of the sample at -3 ° C, So stored below the cloud point. At weekly intervals, the Samples heated to 12 ° C, 50 ml taken for a new CFPP measurement and the remainder stored at -3 ° C on.
  • the dosage rate in test oil 1 was 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A1 + B1 (1: 5) -12 -12 -10 -10 -11 A1 + B2 (1: 3) -13 -16 -12 -15 -14 A2 + B2 (1: 3) -10 -12 -10 -13 -13 A3 + B2 (1: 3) -9 -11 -12 -12 -12 A4 + B1 (1: 4) -12 -13 -11 -12 -10 A5 + B3 (1: 4) -12 -13 -13 -10 -11 B1 (comparison) -10 -4 -5 -3 -4 B2 (comparison) -11 -7 -5 -4 -5 B3 (comparison) -10 -9 -7 -7 -5
  • Test Oil 2 The dosage rate in Test Oil 2 is 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A5 + B3 (1: 4) -13 -14 -15 -11 -12 A1 + B2 (1: 5) -11 -13 -13 -12 -12 B2 (comparison) -10 -9 -7 -8th -5 B3 (comparison) -10 -9 -6 -6 -5
  • An ADT value ⁇ 15 is considered as an indication that the gas oil is satisfactorily usable in "normal" cold weather. Products with ADT values> 25 are referred to as non-filterable. Solubility of the additives ADT Blank value (without additive) 3.0 A5 + B3 (1: 4) 9.4 A1 + B2 (1: 5) 4.8 A1 + B1 (1: 1) 13.3 A2 + B2 (1: 3) 5.2 B2 (comparison) 5.4 B2 + 4% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) 60 B2 + 10% EVA copolymer with 13.5% by weight of vinyl acetate (according to WO 97/17905) not filterable (115 ml in 20 minutes)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (11)

  1. Procédé pour améliorer les propriétés d'écoulement à froid d'huiles combustibles ayant une teneur en soufre inférieure à 500 ppm et une teneur en n-paraffines d'une longueur de chaíne C18 et plus d'au moins 8% en poids, caractérisé par l'addition d'un additif contenant un mélange de
    A) 15% à 50% en poids d'un copolymère d'oléfines inférieures et d'esters vinyliques, composé de
    a) jusqu'à 96% en moles de motifs structurels bivalents de formule 1 -CH2-CR1R2-    dans laquelle R1 et R2 représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe méthyle et
    b) 4% à 10% en moles de motifs structurels bivalents de formule 2
    Figure 00290001
       dans laquelle R3 représente un groupe alkyle en C6 à C16 ramifié saturé qui présente un atome de carbone tertiaire,
    à condition que le copolymère mentionné en A) puisse contenir jusqu'à 5% en poids de comonomères supplémentaires choisis dans le groupe formé par les esters vinyliques, les éthers vinyliques, les esters alkyliques d'acide acrylique, les esters alkyliques d'acide méthacrylique avec des groupes alkyle en C1 à C20, l'isobutylène et des oléfines supérieures contenant au moins 5 atomes de carbone,
    et
    B) 85% à 50% en poids d'au moins un autre copolymère ou terpolymère d'éthylène et d'esters vinyliques ou d'esters d'acide acrylique, qui est à lui seul un agent améliorant l'écoulement à froid.
  2. Procédé selon la revendication 1, caractérisé en ce que R1 et R2 représentent un atome d'hydrogène.
  3. Procédé selon la revendication 1 et/ou 2,
    caractérisé en ce que R3 représente un groupe néoalkyle contenant 7 à 11 atomes de carbone, en particulier un groupe néoalkyle contenant 8, 9 ou 10 atomes de carbone.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce que le copolymère A) contient de préférence 5% à 10% en moles, en particulier 7% à 10% en moles de motifs structurels de formule 2.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que le mélange d'additifs mis en oeuvre présente des viscosités à l'état fondu à 140°C de 20 à 10 000 mPa.s, en particulier de 30 à 5 000 mPa.s, tout particulièrement de 50 à 2 000 mPa.s.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que les copolymères mentionnés en A) ou B) contiennent jusqu'à 5% en poids de comonomères supplémentaires.
  7. Procédé selon la revendication 6, caractérisé en ce que l'on utilise, en tant que comonomères supplémentaires, des esters vinyliques, des éthers vinyliques, des esters alkyliques d'acide acrylique, des esters alkyliques d'acide méthacrylique, de l'isobutylène ou des oléfines supérieures contenant au moins 5 atomes de carbone, de préférence l'hexène, le 4-méthylpentène, l'octène ou le diisobutylène.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce que l'on ajoute des dispersants de paraffine et/ou des polymères en peigne en tant que composants supplémentaires dans la composition d'additifs.
  9. Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que les mélanges d'additifs contiennent 20% à 40% en poids de composant A) et 60% à 80% en poids de composant B).
  10. Additif destiné à améliorer les propriétés d'écoulement à froid d'huiles minérales et de distillats d'huiles minérales, contenant un mélange de
    A) 15% à 50% en poids d'un copolymère d'oléfines inférieures et d'esters vinyliques, composé de
    a) jusqu'à 96% en moles de motifs structurels bivalents de formule 1 -CH2-CR1R2-    dans laquelle R1 et R2 représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe méthyle et
    b) 4% à 10% en moles de motifs structurels bivalents de formule 2
    Figure 00320001
       dans laquelle R3 représente un groupe alkyle en C6 à C16 ramifié saturé qui présente un atome de carbone tertiaire,
    à condition que le copolymère mentionné en A) puisse contenir jusqu'à 5% en poids de comonomères supplémentaires choisis dans le groupe formé par les esters vinyliques, les éthers vinyliques, les esters alkyliques d'acide acrylique, les esters alkyliques d'acide méthacrylique avec des groupes alkyle en C1 à C20, l'isobutylène et les oléfines supérieures contenant au moins 5 atomes de carbone,
    et
    B) 85% à 50% en poids d'au moins un autre copolymère ou terpolymère d'éthylène et d'esters vinyliques ou d'esters d'acide acrylique, qui est à lui seul un agent améliorant l'écoulement à froid et qui présente une teneur en comonomères de 10% à 20% en moles.
  11. Composition d'huile combustible contenant une huile combustible ayant une teneur en soufre inférieure à 500 ppm et une teneur en n-paraffines d'une longueur de chaíne C18 et plus d'au moins 8% en poids et un additif contenant un mélange de
    A) 15% à 50% en poids d'un copolymère d'oléfines inférieures et d'esters vinyliques composé de
    a) jusqu'à 96% en moles de motifs structurels bivalents de formule 1 -CH2-CR1R2-    dans laquelle R1 et R2 représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe méthyle et
    b) 4% à 10% en moles de motifs structurels bivalents de formule 2
    Figure 00330001
       dans laquelle R3 représente un groupe alkyle en C6 à C16 ramifié saturé qui présente un atome de carbone tertiaire,
    à condition que le copolymère mentionné en A) puisse contenir jusqu'à 5% en poids de comonomères supplémentaires choisis dans le groupe formé par les esters vinyliques, les éthers vinyliques, les esters alkyliques d'acide acrylique, les esters alkyliques d'acide méthacrylique avec des groupes alkyle en C1 à C20, l'isobutylène et les oléfines supérieures contenant au moins 5 atomes de carbone,
    et
    B) 85% à 50% en poids d'au moins un autre copolymère ou terpolymère d'éthylène et d'esters vinyliques ou d'esters d'acide acrylique, qui est à lui seul un agent améliorant l'écoulement à froid et qui présente une teneur en comonomères de 10% à 20% en moles.
EP98124678A 1998-01-24 1998-12-24 Procédés d'amélioration des propriétés d'écoulement à froid d'huiles combustibles Expired - Lifetime EP0931824B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19802690A DE19802690C2 (de) 1998-01-24 1998-01-24 Additiv zur Verbesserung der Kaltfließeigenschaften von Brennstoffölen
DE19802690 1998-01-24

Publications (3)

Publication Number Publication Date
EP0931824A2 EP0931824A2 (fr) 1999-07-28
EP0931824A3 EP0931824A3 (fr) 1999-09-15
EP0931824B1 true EP0931824B1 (fr) 2005-08-31

Family

ID=7855580

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98124678A Expired - Lifetime EP0931824B1 (fr) 1998-01-24 1998-12-24 Procédés d'amélioration des propriétés d'écoulement à froid d'huiles combustibles

Country Status (8)

Country Link
US (1) US6110238A (fr)
EP (1) EP0931824B1 (fr)
JP (1) JP4370011B2 (fr)
AT (1) ATE303426T1 (fr)
CA (1) CA2260169C (fr)
DE (2) DE19802690C2 (fr)
ES (1) ES2248874T3 (fr)
NO (1) NO990293L (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19729057A1 (de) * 1997-07-08 1999-01-14 Clariant Gmbh Copolymere auf Basis von Ethylen und ungesättigten Carbonsäureestern und ihre Verwendung als Mineralöladditive
DE19754555A1 (de) * 1997-12-09 1999-06-24 Clariant Gmbh Verfahren zur Herstellung von Ethylen-Mischpolymerisaten und deren Verwendung als Zusatz zu Mineralöl und Mineralöldestillaten
DE10012269C2 (de) 2000-03-14 2003-05-15 Clariant Gmbh Verwendung von Copolymermischungen als Additiv zur Verbesserung der Kaltfließeigenschaften von Mitteldestillaten
DE10012267B4 (de) 2000-03-14 2005-12-15 Clariant Gmbh Copolymermischungen und ihre Verwendung als Additiv zur Verbesserung der Kaltfließeigenschaften von Mitteldestillaten
WO2002090470A1 (fr) * 2001-05-08 2002-11-14 Sanyo Chemical Industries, Ltd. Agent fluidifiant et composition de mazout
DE10208326B4 (de) * 2002-02-27 2008-06-19 Innospec Deutschland Gmbh Additive für flüssige Kraftstoffe
DE10245737C5 (de) * 2002-10-01 2011-12-08 Clariant Produkte (Deutschland) Gmbh Verfahren zur Herstellung von Additivmischungen für Mineralöle und Mineralöldestillate
DE10260714A1 (de) * 2002-12-23 2004-07-08 Clariant Gmbh Brennstofföle mit verbesserten Kälteeigenschaften
DE102006022720B4 (de) * 2006-05-16 2008-10-02 Clariant International Limited Kaltfließverbesserer für pflanzliche oder tierische Brennstofföle
FR2947558B1 (fr) 2009-07-03 2011-08-19 Total Raffinage Marketing Terpolymere et ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles
CN110312886B (zh) 2018-01-25 2023-03-28 巴西石油公司 用于开始或重新开始凝胶化流体的流动的辅助系统和方法

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048479A (en) * 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates
DE1914756C3 (de) * 1968-04-01 1985-05-15 Exxon Research and Engineering Co., Linden, N.J. Verwendung von Ethylen-Vinylacetat- Mischpolymerisaten für Erdöl-Destillate
DE2037673C2 (de) * 1970-07-16 1985-07-04 Exxon Research and Engineering Co., Linden, N.J. Polymerisatgemische als Fließpunktverbesserer für Kohlenwasserstoffe und deren Verwendung
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
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
GB8300016D0 (en) * 1983-01-04 1983-02-09 Exxon Research Engineering Co Middle distillate compositions
DE3405843A1 (de) * 1984-02-17 1985-08-29 Bayer Ag, 5090 Leverkusen Copolymere auf basis von maleinsaeureanhydrid und (alpha), (beta)-ungesaettigten verbindungen, ein verfahren zu ihrer herstellung und ihre verwendung als paraffininhibitoren
DE3584729D1 (de) * 1984-02-21 1992-01-09 Exxon Research Engineering Co Mitteldestillat-zusammensetzungen mit fliesseigenschaften bei kaelte.
DE3625174A1 (de) * 1986-07-25 1988-01-28 Ruhrchemie Ag Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
DE3640613A1 (de) * 1986-11-27 1988-06-09 Ruhrchemie Ag Verfahren zur herstellung von ethylen-mischpolymerisaten und deren verwendung als zusatz zu mineraloel und mineraloelfraktionen
DE3742630A1 (de) * 1987-12-16 1989-06-29 Hoechst Ag Polymermischungen fuer die verbesserung der fliessfaehigkeit von mineraloeldestillaten in der kaelte
DE3926992A1 (de) * 1989-08-16 1991-02-21 Hoechst Ag Verwendung von umsetzungsprodukten von alkenylspirobislactonen und aminen als paraffindispergatoren
DE4042206A1 (de) * 1990-12-29 1992-07-02 Hoechst Ag Terpolymerisate des ethylens, ihre herstellung und ihre verwendung als additive fuer mineraloeldestillate
GB9213909D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
US5718734A (en) * 1992-06-30 1998-02-17 Exxon Chemical Patents Inc. Oil additives and compositions
GB9213904D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
GB9213854D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Additives and fuel compositions
GB9213870D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
DE59404053D1 (de) * 1993-01-06 1997-10-23 Hoechst Ag Terpolymere auf Basis von alpha,beta-ungesättigten Dicarbonsäureanhydriden, alpha,beta-ungesättigten Verbindungen und Polyoxyalkylenethern von niederen, ungesättigten Alkoholen
GB9417670D0 (en) * 1994-09-02 1994-10-19 Exxon Chemical Patents Inc Oil additives, compositions and polymers for use therein
GB9424565D0 (en) * 1994-12-06 1995-01-25 Exxon Chemical Patents Inc Fuel oil compositions
EP1050573A3 (fr) * 1994-12-13 2001-01-03 Infineum USA L.P. Compositions d'huile combustible
GB9508644D0 (en) * 1995-04-28 1995-06-14 Exxon Chemical Patents Inc Fuel compositions
DE19620118C1 (de) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymerisate des Ethylens, ihre Herstellung und ihre Verwendung als Additive für Mineralöldestillate
DE19620119C1 (de) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymerisate des Ethylens, ihre Herstellung und ihre Verwendung als Additive für Mineralöldestillate
DE19729055C2 (de) * 1997-07-08 2000-07-27 Clariant Gmbh Brennstofföle auf Basis von Mitteldestillaten und Copolymeren aus Ethylen und ungesättigten Carbonsäureestern
DE19758887A1 (de) * 1997-07-08 2006-10-19 Clariant Gmbh Fließverbesserer für Mineralöle

Also Published As

Publication number Publication date
JP4370011B2 (ja) 2009-11-25
ES2248874T3 (es) 2006-03-16
CA2260169C (fr) 2008-09-16
US6110238A (en) 2000-08-29
EP0931824A2 (fr) 1999-07-28
JPH11256171A (ja) 1999-09-21
NO990293L (no) 1999-07-26
DE19802690A1 (de) 1999-07-29
NO990293D0 (no) 1999-01-22
DE19802690C2 (de) 2003-02-20
ATE303426T1 (de) 2005-09-15
CA2260169A1 (fr) 1999-07-24
DE59813030D1 (de) 2005-10-06
EP0931824A3 (fr) 1999-09-15

Similar Documents

Publication Publication Date Title
EP0922716B1 (fr) Procédé de préparation de terpolymères d'éthylène et leur utilisation comme additifs à l'huile minérale et aux distillats d'huile minérale
EP0807642B1 (fr) Terpolymères de l'éthylène, leur préparation et leur utilisation pour les distillats d'huile minérale
EP0398101B1 (fr) Produits de réaction d'acides aminoalkylène-polycarboxyliques avec des amines secondaires ainsi que distillats moyens de pétrole brut les contenant
EP0931825B1 (fr) Procédé et une composition d'amélioration des propriétés d'écoulement à froid d'huiles combustibles
EP1146108B1 (fr) Mélanges de copolymères et leurs utilisations comme additif pour l'amélioration des propriétés d'écoulement à froid de distillats moyens
DE10260714A1 (de) Brennstofföle mit verbesserten Kälteeigenschaften
EP0931824B1 (fr) Procédés d'amélioration des propriétés d'écoulement à froid d'huiles combustibles
EP1022293B1 (fr) Copolymères et leur utilisation pour l'amélioration des propriétés d'écoulement à froid des distillats moyens
DE19848621A1 (de) Paraffindispergatoren mit Lubricity-Wirkung für Erdölmitteldestillate
EP0900836A1 (fr) Additif pour améliorer l'écoulement d'huiles minérales et de distallats d'huile minérale
EP0890589B1 (fr) Solutions ou dispersions à base de copolymres d'oléfines et d'esters d'acides carboxyliques non saturés et leur utilisation comme additifs pour des huiles minérales
DE10012269C2 (de) Verwendung von Copolymermischungen als Additiv zur Verbesserung der Kaltfließeigenschaften von Mitteldestillaten
EP0892012B1 (fr) Agent améliorant l'ecoulement d'huiles minerales
EP0890633B1 (fr) Utilisation de copolymères d'éthylène et d'esters carboxyliques insaturés dans des distillats moyens pour l'amélioration des propriétés d'écoulement à froid

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FI FR GB GR IT LI NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RIC1 Information provided on ipc code assigned before grant

Free format text: 6C 10L 1/18 A, 6C 10L 1/14 B, 6C 08L 23/08 B

17P Request for examination filed

Effective date: 20000315

AKX Designation fees paid

Free format text: AT BE CH DE DK ES FI FR GB GR IT LI NL PT SE

17Q First examination report despatched

Effective date: 20020625

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RBV Designated contracting states (corrected)

Designated state(s): AT BE DE ES FR GB NL SE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB NL SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59813030

Country of ref document: DE

Date of ref document: 20051006

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20051116

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2248874

Country of ref document: ES

Kind code of ref document: T3

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

Effective date: 20060315

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060601

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

BECN Be: change of holder's name

Owner name: *CLARIANT PRODUKTE DEUTSCHLAND G.M.B.H.

Effective date: 20050831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20081021

Year of fee payment: 11

Ref country code: AT

Payment date: 20081020

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091224

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110322

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091225

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20161021

Year of fee payment: 19

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20171226

Year of fee payment: 20

Ref country code: NL

Payment date: 20171221

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20171228

Year of fee payment: 20

Ref country code: BE

Payment date: 20171221

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20180228

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171225

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59813030

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20181223

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20181223

REG Reference to a national code

Ref country code: BE

Ref legal event code: MK

Effective date: 20181224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20181223