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EP0890633B1 - Verwendung von Copolymeren aus Ethylen und ungesättigten Carbonsäureestern in Mitteldestillaten zur Verbesserung der Kaltfliesseigenschaften - Google Patents

Verwendung von Copolymeren aus Ethylen und ungesättigten Carbonsäureestern in Mitteldestillaten zur Verbesserung der Kaltfliesseigenschaften Download PDF

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Publication number
EP0890633B1
EP0890633B1 EP98111799A EP98111799A EP0890633B1 EP 0890633 B1 EP0890633 B1 EP 0890633B1 EP 98111799 A EP98111799 A EP 98111799A EP 98111799 A EP98111799 A EP 98111799A EP 0890633 B1 EP0890633 B1 EP 0890633B1
Authority
EP
European Patent Office
Prior art keywords
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mol
copolymers
structural units
carbon atoms
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
EP98111799A
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German (de)
English (en)
French (fr)
Other versions
EP0890633A1 (de
Inventor
Matthias Dr. Krull
Werner Dr. Reimann
Markus Kupetz
Waltraud Nagel
Raimund Wildfang
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Anticipated expiration legal-status Critical
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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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof 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 a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof 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 a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

  • the present invention relates to fuel oils, the middle distillates and copolymers of ethylene and Contain esters of unsaturated carboxylic acids, and which show improved cold flow behavior.
  • Crude oils and middle distillates obtained by distilling crude oils such as gas oil, diesel oil or heating oil contain different amounts of n-paraffins depending on the origin of the crude oils, crystallize the temperature as platelet-shaped crystals and partially with the inclusion of oil agglomerate. This leads to a deterioration in the flow properties of these oils or Distillates, which, for example, during the extraction, transport, storage and / or use of Mineral oils and mineral oil distillates can occur. With mineral oils this can Crystallization phenomenon during transport through pipelines, especially in winter, leads to deposits the pipe walls, in individual cases, e.g. if a pipeline is at a standstill, even to completely block it to lead.
  • the flow and cold behavior of mineral oils and mineral oil distillates is determined by specifying the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116) described. Both parameters are measured in ° C.
  • Typical flow improvers for crude oils and middle distillates are copolymers of ethylene with Carboxylic acid ester of vinyl alcohol. So according to DE-A-11 47 799 petroleum distillate propellant or fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers from ethylene and vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers containing about 60 to 99% by weight of ethylene and about 1 to 40% by weight are preferred. Contain vinyl acetate. They are particularly effective when used in radical polymerization an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 were manufactured (DE-A-1914 756).
  • copolymers based on ⁇ , ⁇ -unsaturated compounds and Maleic anhydride used as a flow improver.
  • DE-196 45 603 describes copolymers of 60 to 99 mol% derived from ethylene Structural units and 1 to 40 mol% of structural units that differ from maleic acid, its Derive anhydride or its imides.
  • DE-1 162 630 discloses copolymers of ethylene and vinyl esters of straight-chain fatty acids 4 to 18 carbon atoms as a pour point reducing additive for distillate fuels of medium size Siedelage such as Hiezöl or diesel oil.
  • EP-A-0 217 602 discloses ethylene copolymers with vinyl esters bearing C 1 to C 18 alkyl radicals as flow improvers for mineral oil distillates with boiling ranges (90-20)% below 100 ° C.
  • EP-A-0 493 769 discloses terpolymers which consist of ethylene, vinyl acetate and neononane or Neodecanoic acid vinyl esters are produced, and their use as additives for Mineratöldestillate.
  • EP-A-0 746 598 discloses copolymers of ethylene and di-alkyl fumarates mixed with Mineral oils with a cloud point below -10 ° C.
  • the main problems are those for use under arctic conditions produced winter qualities of diesel fuels with their extreme Katte properties, such as a cloud point below -8 ° C and especially below -15 ° C, very much narrow distillation cuts with boiling ranges from 20 to 90 vol .-% less than 120 ° C, in particular less than 100 ° C and sometimes also less than 80 ° C, and a distillation volume of 95% by volume Temperatures below 360 ° C, especially below 350 ° C and especially below 330 ° C.
  • the Cold properties of such distillates can currently only be achieved by adding low-boiling, low-paraffin components, e.g. Kerosene, can be improved satisfactorily.
  • composition caused by narrow distillation cuts and low boiling ends is problematic for the response behavior of flow improvers to these oils:
  • These oils have a paraffin distribution with a maximum at around C 12 to C 14 and contain only insignificant amounts of the n-paraffins with hydrocarbon chains that crystallize from conventional grades longer as C 18 .
  • the cloud points and CFPP values are so low, especially in terms of winter qualities, that conventional flow improvers do not respond and the properties of the liquid have to be adjusted by diluting with kerosene.
  • the cloud point of the mineral oils mentioned under A) is preferably below -15 ° C.
  • the boiling ranges (90-20%) of the distillation cuts are preferably less than 100 ° C., in particular less than 80 ° C. It is preferred to use mineral oils with a 95% distillation point below 360 ° C, especially below 350 ° C, especially below 330 ° C.
  • R 1 is preferably hydrogen.
  • R 3 preferably represents a linear or branched C 8 -C 18 alkyl radical.
  • R denotes a neoalkyl radical with 7 to 11 carbon atoms, in particular a neoalkyl radical with 8, 9 or 10 carbon atoms.
  • the neoalkyl acids from which the above-mentioned neoalkyl radicals can be derived are described by the formula (3):
  • R 'and R are linear alkyl radicals with a total of preferably 5 to 9, in particular 6, 7 or 8, carbon atoms.
  • the vinyl ester used for the copolymerization accordingly has the formula (4):
  • Suitable comonomers are those which can be derived from acrylic acid:
  • Preferred radicals R 3 are, for example, butyl, tert-butyl, pentyl, neopentyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and behenyl.
  • the fuel oil compositions according to the invention preferably contain copolymers in which the comonomers B1) with 90 to 96 mol% and the comonomers B2) with 4 to 10 mol% are included.
  • the copolymers mentioned under B) are as usual by the usual copolymerization for example suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure mass polymerization.
  • The is preferred High pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 300, in particular 100 to 250 ° C.
  • the reaction of the Monomers are initiated by radical initiators (radical chain initiators).
  • radical initiators radical chain initiators
  • 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 permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances Amounts of 0.001 to 20 wt .-%, preferably 0.01 to 10 wt .-%, based on the Monomer mixture used.
  • the copolymers mentioned under B) preferably have melt viscosities at 140 ° C. of 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
  • the desired Melt viscosity of these copolymers is given the given composition of Monomer mixture by varying the reaction parameters pressure and temperature and possibly by adding moderators.
  • the moderators are hydrogen, saturated or unsaturated hydrocarbon, e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g.
  • the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight the mixture of monomers applied.
  • the copolymers mentioned under B) can contain up to 3 mol% of vinyl acetate or up to 5 mol% of more Comonomers included.
  • Such comonomers can, for example, vinyl esters, vinyl ethers, Acrylic acid alkyl esters, methacrylic acid alkyl esters or higher olefins with at least 5 Be carbon atoms. Hexene, 4-methylpentene, octene or are preferred as higher olefins Diisobutylene.
  • monomer mixtures which in addition to ethylene and optionally a moderator 1 to 50% by weight, preferably 3 to 40% by weight Comonomer included.
  • a moderator 1 to 50% by weight preferably 3 to 40% by weight Comonomer included.
  • the composition of the monomer mixture is carried by the different ones Polymerization rate of the monomers calculation.
  • the polymers fall as colorless Melt, which solidify to waxy solids at room temperature.
  • High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or Tube reactors, carried out batchwise or continuously, have proven particularly useful Tubular reactors.
  • Solvents such as aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, benzene or toluene can be contained in the reaction mixture.
  • the solvent-free mode of operation is preferred.
  • the Polymerization is the mixture of the monomers, the initiator and, if used, the Moderator, a tubular reactor via the reactor inlet and one or more side branches fed.
  • the monomer streams can have different compositions here (EP-A-0 271 738).
  • the copolymers mentioned under B) are the mineral oils mentioned under A) or Mineral oil distillates added in the form of solutions or dispersions. These solutions or Dispersions preferably contain 1 to 90, in particular 10 to 80,% by weight of the copolymers.
  • Suitable solvents or dispersing agents 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 solvents Naphtha, "" Shellsol AB, "Solvesso 150," Solvesso 200, “Exxsol,” ISOPAR and "Shellsol D types.
  • the Fuel oils according to the invention preferably contain 0.001 to 2, in particular 0.005 to 0.5 % By weight of copolymer, based on the distillate.
  • the fuel oils of the invention may contain other oil-soluble co-additives that are already for only the flow properties of crude oils, lubricating oils or fuel oils improve.
  • co-additives are copolymers containing vinyl acetate or terpolymers of ethylene, polar compounds which effect paraffin dispersion (paraffin dispersants), and Comb polymers.
  • Oil-soluble polar compounds with ionic or polar have been found as paraffin dispersants Groups, e.g. Amine salts and / or amides proven by the reaction aliphatic or aromatic Amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, Tri- or tetracarboxylic acids or their anhydrides are obtained (cf. US-4 211 534).
  • paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated Compounds optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf.
  • EP-A-0 154 177 the reaction products of alkenylspirobislactones with amines (cf. EP-A-0 413 279) and according to EP-A-0 606 055, reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated Compounds and polyoxyalkenyl ethers of lower unsaturated alcohols.
  • 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. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers - Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of 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. EP- A-0 320 766), furthermore esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • the new fuel oils can contain other additives, for example Dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives or Sludge inhibitors.
  • Table 3 shows the effectiveness of the additives as flow improvers for mineral oil distillates using the CFPP test (Cold Filter Plugging Test according to EN 116) in various distillates from Scandinavian refineries.
  • the additives are used as 50% solutions in solvent naphtha.
  • EVA copolymer ethylene-vinyl acetate copolymer
  • V1 melt viscosity V 140 of 125 mPas
  • V2 melt viscosity
  • Test oil 1 Test oil 4
  • Test oil 5 Test oil 6
  • the CFPP is determined according to EN116, the PP according to ISO 3016 with an automatic device (Herzog MC 852).

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  • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP98111799A 1997-07-08 1998-06-26 Verwendung von Copolymeren aus Ethylen und ungesättigten Carbonsäureestern in Mitteldestillaten zur Verbesserung der Kaltfliesseigenschaften Expired - Lifetime EP0890633B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19729055 1997-07-08
DE19729055A DE19729055C2 (de) 1997-07-08 1997-07-08 Brennstofföle auf Basis von Mitteldestillaten und Copolymeren aus Ethylen und ungesättigten Carbonsäureestern

Publications (2)

Publication Number Publication Date
EP0890633A1 EP0890633A1 (de) 1999-01-13
EP0890633B1 true EP0890633B1 (de) 2004-03-17

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EP98111799A Expired - Lifetime EP0890633B1 (de) 1997-07-08 1998-06-26 Verwendung von Copolymeren aus Ethylen und ungesättigten Carbonsäureestern in Mitteldestillaten zur Verbesserung der Kaltfliesseigenschaften

Country Status (5)

Country Link
EP (1) EP0890633B1 (ja)
JP (1) JP4754664B2 (ja)
AT (1) ATE262021T1 (ja)
CA (1) CA2242517C (ja)
DE (2) DE19729055C2 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19802690C2 (de) * 1998-01-24 2003-02-20 Clariant Gmbh Additiv zur Verbesserung der Kaltfließeigenschaften von Brennstoffölen
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
DE10349851B4 (de) * 2003-10-25 2008-06-19 Clariant Produkte (Deutschland) Gmbh Kaltfließverbesserer für Brennstofföle pflanzlichen oder tierischen Ursprungs
JP4520160B2 (ja) * 2004-01-08 2010-08-04 東邦化学工業株式会社 燃料油用流動性向上剤
DK2235145T3 (da) 2007-12-20 2019-05-20 Shell Int Research Brændstofsammensætninger
JP2011508000A (ja) 2007-12-20 2011-03-10 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 燃料組成物
WO2009080679A1 (en) * 2007-12-20 2009-07-02 Shell Internationale Research Maatschappij B.V. Process to prepare a gas oil and a base oil

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Also Published As

Publication number Publication date
ATE262021T1 (de) 2004-04-15
DE59810973D1 (de) 2004-04-22
JPH1171587A (ja) 1999-03-16
JP4754664B2 (ja) 2011-08-24
CA2242517A1 (en) 1999-01-08
EP0890633A1 (de) 1999-01-13
DE19729055A1 (de) 1999-01-14
CA2242517C (en) 2007-05-29
DE19729055C2 (de) 2000-07-27

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