EP0190553B1 - Procédé d'amélioration de la fluidité des huiles minérales et des distillats d'huiles minérales - Google Patents

Procédé d'amélioration de la fluidité des huiles minérales et des distillats d'huiles minérales Download PDF

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Publication number
EP0190553B1
EP0190553B1 EP86100143A EP86100143A EP0190553B1 EP 0190553 B1 EP0190553 B1 EP 0190553B1 EP 86100143 A EP86100143 A EP 86100143A EP 86100143 A EP86100143 A EP 86100143A EP 0190553 B1 EP0190553 B1 EP 0190553B1
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EP
European Patent Office
Prior art keywords
ethylene
vinylacetate
vinyl acetate
propene
process according
Prior art date
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Expired
Application number
EP86100143A
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German (de)
English (en)
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EP0190553A1 (fr
Inventor
Wolfgang Dr. Dipl.Chem. Payer
Ludger Dr. Dipl.Chem. Bexten
Hans-Albert Lümmen
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Ruhrchemie AG
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Ruhrchemie AG
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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
    • C10L1/197—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/08—Pipe-line systems for liquids or viscous products
    • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
    • F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting

Definitions

  • the present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-propene-vinyl acetate terpolymers.
  • Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. So z. B. the working ability of production and transport facilities for crude oil are impaired until their complete failure. In diesel engines and combustion plants, the filters can become blocked, which ultimately results in an interruption in the fuel or heating medium supply.
  • additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.
  • Copolymers of ethylene with carboxylic acid esters of vinyl alcohol have achieved the greatest importance as pour point depressants and flow improvers for crude oils and middle distillates.
  • ethylene-vinyl acetate copolymers have proven particularly useful.
  • Such copolymers and their use are e.g. B. described in DE-C-1 914 756. They are generally prepared by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C. and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.
  • Ethylene-vinyl acetate copolymers are generally commercially available as solutions in hydrocarbons. For economic reasons, these solutions should contain the active ingredient in the highest possible concentration and be easy to handle.
  • the invention consists in a process for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that a mixture of an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates.
  • the ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate (based in each case on the copolymer) have proven particularly useful. Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, measured at 140 ° C. in each case, and they each have 100 CH 2 groups 2 to 10, in particular 3 to 7 CH 3 groups.
  • the production of the ethylene-vinyl acetate copolymers is known. It is carried out by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in an organic solvent as the reaction medium. However, the polymerization is preferably carried out at pressures above 50 MPa and temperatures between 120 and 300 ° C. in the absence of organic solvents.
  • the ethylene-propene-vinyl acetate terpolymers of the new process contain 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate (in each case based on the terpolymer).
  • Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C.
  • Each 100 CH 2 groups have 8 to 25, in particular 12 to 20 CH 3 groups, which do not result from the acetate residue of the vinyl acetate.
  • the preparation of the terpolymers is also described.
  • Mixtures of ethylene, propene and vinyl acetate are used, which are polymerized in the presence of free radical initiators at pressures above 50 mPa and at temperatures from 150 to 350 ° C. in the absence of organic solvents.
  • the molecular weight of the terpolymers is preferably adjusted by the propene, which also acts as a molecular weight regulator.
  • other molecular weight regulators such as hydrocarbons, aldehydes, ketones can also be used.
  • Monomer mixtures containing 30 to 60% by weight of ethylene, 20 to 50% by weight of propene and 15 to 35% by weight of vinyl acetate are used for the polymerization.
  • the mineral oils and mineral oil distillates produced by the process according to the invention to improve their flowability are added to polymer mixtures containing ethylene-vinyl acetate.
  • Copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5 to 1 to 20 to 1.
  • Preference is given to mixtures which contain the copolymer and terpolymer in a weight ratio of 2 to 1 to 10 to 1.
  • the viscosity of the polymers contained in the mixture should also be as equal as possible, and the deviations should in particular not be greater than 200 mPa.s, measured at 140 ° C.
  • the mixtures of the polymers are added to the mineral oils or the mineral oil fractions in the form of 40 to 60% by weight solutions in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture.
  • Z is particularly suitable.
  • the amount of polymer, based on mineral oil or mineral oil fraction, should be 0.001 to 2, preferably 0.005 to 0.5% by weight.
  • the polymer mixtures can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, corrosion inhibitors, antioxidants or sludge inhibitors.
  • Examples AF relate to the preparation of the ethylene-propene-vinyl acetate terpolymers
  • examples G-I relate to the production of the ethylene-vinyl acetate copolymers.
  • Examples 1-6 summarize the effectiveness of the terpolymers, examples 7-9 show the effectiveness of the copolymers as flow improvers.
  • Examples 10-18 describe the flow behavior of middle distillates after the addition of copolymer-terpolymer mixtures according to the inventive method.
  • Ethylene, propene and vinyl acetate are continuously polymerized in an autoclave.
  • the monomer mixture is fed into the autoclave at the reaction pressure after the amount of peroxide required to maintain the polymerization has been added as a solution in a gasoline fraction.
  • the dwell time is about 80 seconds.
  • the vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask at 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with a NaJ / KJ0 3 solution and the released iodine is titrated with Na 2 S 2 0 3 solution.
  • the degree of branching of the polymers is determined by H-NMR spectroscopy.
  • the degree of branching is understood to mean the number of CH 3 groups per 100 CH 2 groups with the exception of the CH 3 groups, which originate from the acetate residue.
  • the monomer mixture consisting of ethylene and vinyl acetate is polymerized in a tubular reactor at 150 MPa pressure in the absence of substantial amounts of a solvent.
  • Organic peroxides are used as initiators.
  • the vinyl acetate content and the degree of branching are determined by the methods given for the ethylene-propene-vinyl acetate terpolymers.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (10)

1. Procédé pour l'amélioration de la fluidité des huiles minérales et des distillats d'huiles minérales, caractérisé en ce que l'on ajoute aux huiles minérales ou distillats d'huiles minérales un mélange d'un copolymère éthylène-acétate de vinyle et d'un terpolymère éthylène-propène-acétate de vinyle.
2. Procédé selon la revendication 1, caractérisé en ce que le copolymère éthylène-acétate de vinyle contient 20 à 40 % en poids d'acétate de vinyle, en particulier 25 à 35 % en poids.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que le copolymère d'acétate de vinyle possède une viscosité de 100 à 5 000 mPa.s, en particulier de 200 à 1 500 mPa.s, mesurée chaque fois à 140°c.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que le copolymère d'acétate de vinyle présente pour 100 groupes CH2 de 2 à 10 groupes CH3, en particulier de 3 à 7 groupes CH3, ne provenant pas du reste acétate de l'acétate de vinyle.
5. Procédé selon la revendication 1, caractérisé en ce que le terpolymère éthylène-propène-acétate de vinyle contient 20 à 40 % en poids d'acétate de vinyle, en particulier 25 à 35 % en poids.
6. Procédé selon les revendications 1 et 5, caractérisé en ce que la viscosité du terpolymère éthylène-propène-acétate de vinyle est de 100 à 5 000 mPa.s, en particulier de 200 à 1 500 mPa.s, mesurée chaque fois à 140° C.
7. Procédé selon les revendications 1, 5 et 6, caractérisé en ce que le terpolymère éthylène-propène-acétate de vinyle contient pour 100 groupes CH2 de 8 à 25 groupes CH3, en particulier de 12 à 20 groupes CH3 ne provenant pas du reste acétate de l'acétate de vinyle.
8. Procédé selon les revendications 1 à 7, caractérisé en ce que le mélange de polymères contient le copolymère éthylèneacétate de vinyle et le terpolymère éthylène-propène-acétate de vinyle dans un rapport pondéral de 0,5 : 1 à 20 : 1, en particulier de 2 : 1 à 10 : 1.
9. Procédé selon les revendications 1 à 8, caractérisé en ce que les teneurs en acétate de vinyle du copolymère et du terpolymère dans le mélange de polymères ne s'écartent pas l'une de l'autre de plus de 3 % en poids, en valeur absolue.
10. Procédé selon les revendications 1 à 9, caractérisé en ce que les viscosités des copolymères contenus dans le mélange ne s'écartent pas l'une de l'autre de plus de 200 mPa.s, mesurées à 140°C.
EP86100143A 1985-01-17 1986-01-08 Procédé d'amélioration de la fluidité des huiles minérales et des distillats d'huiles minérales Expired EP0190553B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853501384 DE3501384A1 (de) 1985-01-17 1985-01-17 Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
DE3501384 1985-01-17

Publications (2)

Publication Number Publication Date
EP0190553A1 EP0190553A1 (fr) 1986-08-13
EP0190553B1 true EP0190553B1 (fr) 1988-05-18

Family

ID=6260051

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EP86100143A Expired EP0190553B1 (fr) 1985-01-17 1986-01-08 Procédé d'amélioration de la fluidité des huiles minérales et des distillats d'huiles minérales

Country Status (2)

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EP (1) EP0190553B1 (fr)
DE (2) DE3501384A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3621395A1 (de) * 1986-06-26 1988-01-28 Ruhrchemie Ag Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
DE3625174A1 (de) * 1986-07-25 1988-01-28 Ruhrchemie Ag Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
GB9213871D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
DE19821736A1 (de) * 1998-05-14 1999-11-18 Wacker Chemie Gmbh Verfahren zur Herstellung von Vinylester-Ethylen-Mischpolymerisaten mit reduzierter Oberflächenklebrigkeit
GB0506795D0 (en) * 2005-04-04 2005-05-11 Agt Energy Ltd Wax-containing materials
DE102006033151B4 (de) * 2006-07-18 2014-11-20 Clariant International Limited Additive zur Verbesserung der Kälteeigenschaften von Brennstoffölen
DE102006033150B4 (de) * 2006-07-18 2008-10-16 Clariant International Limited Additive zur Verbesserung der Kälteeigenschaften von Brennstoffölen
DE102006033149A1 (de) 2006-07-18 2008-01-31 Clariant International Limited Additive zur Verbesserung der Kälteeigenschaften von Brennstoffölen

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1914756C3 (de) 1968-04-01 1985-05-15 Exxon Research and Engineering Co., Linden, N.J. Verwendung von Ethylen-Vinylacetat- Mischpolymerisaten für Erdöl-Destillate
US3661541A (en) * 1969-04-22 1972-05-09 Exxon Research Engineering Co Fuel oil compositions containing a mixture of polymers to improve the pour point and flow properties
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
EP0003489B1 (fr) * 1977-12-20 1983-01-12 Imperial Chemical Industries Plc Huile brute ayant des propriétés améliorées d'écoulement à froid
US4354011A (en) * 1978-10-02 1982-10-12 Exxon Research & Engineering Co. Copolymers of ethylene and ethylenically unsaturated monomers, process for their preparation and distillate oil containing said copolymers
US4178951A (en) * 1978-10-10 1979-12-18 Texaco Inc. Low pour point crude oil compositions
DD161128A1 (de) * 1980-03-03 1985-02-20 Leuna Werke Veb Verfahren zur herstellung eines fliessverbesserers
JPH0710900B2 (ja) * 1982-06-18 1995-02-08 エクソン リサーチ アンド エンヂニアリング コムパニー 中級蒸留物燃料油用流動性改良剤

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Publication number Publication date
DE3660207D1 (en) 1988-06-23
DE3501384A1 (de) 1986-07-17
EP0190553A1 (fr) 1986-08-13

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