EP0251002B1 - Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales - Google Patents

Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales Download PDF

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Publication number
EP0251002B1
EP0251002B1 EP87108559A EP87108559A EP0251002B1 EP 0251002 B1 EP0251002 B1 EP 0251002B1 EP 87108559 A EP87108559 A EP 87108559A EP 87108559 A EP87108559 A EP 87108559A EP 0251002 B1 EP0251002 B1 EP 0251002B1
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EP
European Patent Office
Prior art keywords
vinyl acetate
ethylene
mineral oil
acetate copolymer
oxidised
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
EP87108559A
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German (de)
English (en)
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EP0251002A1 (fr
Inventor
Wolfgang Dr. Dipl.-Chem. Payer
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Hoechst AG
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Hoechst AG
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Priority to AT87108559T priority Critical patent/ATE58749T1/de
Publication of EP0251002A1 publication Critical patent/EP0251002A1/fr
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers

Definitions

  • the present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of an ethylene-vinyl acetate copolymer and an oxidized polyethylene wax and / or an oxidized ethylene-vinyl acetate copolymer.
  • 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. For example, the working capacity of conveying and transport facilities for crude oil are impaired until their complete failure. In diesel engines and combustion plants, the filters can become clogged, 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 and carboxylic acid esters of vinyl alcohol have become very important 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 described for example in DE-PS 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.
  • the remedy is to add large quantities or to mix the mineral oil or mineral oil distillate with low-boiling hydrocarbons.
  • DE 2 639 672 A1 describes mixtures of polymers with an ethylene skeleton and copolymers of C 2 to Cso-olefins which lead to a synergistic improvement in the flow properties of Distillate hydrocarbon oils can lead in the cold.
  • the object described above is achieved by a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that mixtures of an ethylene-vinyl acetate copolymer and an oxidized polyethylene wax and / or an oxidized ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.
  • the ethylene-vinyl acetate copolymers used according to the invention contain 17 to 70 parts by weight of vinyl acetate per 100 parts by weight of ethylene. Copolymers with 33 to 54 parts by weight of vinyl acetate per 100 parts by weight of ethylene have proven particularly useful.
  • Its viscosity measured in accordance with the German standard DIN 53019 in a rotary viscometer (manufacturer: Haake) at 140 ° C, is 100 to 5000 mPa s, in particular 200 to 1500 mPa s.
  • Each 100 CH 2 groups have 1 to 10 and preferably 2 to 7 CH 3 groups in the side chains, which do not result from the acetate residue of the vinyl acetate.
  • the number of CH 3 groups is determined by H-NMR spectroscopy.
  • the production of the ethylene-vinyl acetate copolymers is known. It can be carried out, for example, by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in the presence of initiators which form free radicals.
  • An organic solvent or suspending agent such as toluene can be used as the reaction medium.
  • oxidized polyethylene waxes is understood to mean products which are obtained in the treatment of melts of linear or branched polyethylene waxes with air. These are waxes that contain oxygen functions such as carboxyl, carbonyl, hydroxyl groups in the molecule. They are characterized above all by their emulsifiability in aqueous media.
  • the wax oxidates used according to the invention have melting points of 85 to 135 ° C., dropping points of 95 to 135 ° C. and densities of 0.94 to 1.00 g / cm 3 determined in accordance with DIN 51801 or ASTM D 566.
  • Oxidized ethylene-vinyl acetate copolymers are the products of the oxidation of molten ethylene-vinyl acetate copolymers with oxygen or gases containing oxygen. Their manufacture is described, for example, in DE 2 944 375 AI. According to the invention, oxidized ethylene-vinyl acetate copolymers are used which have dropping points of 80 to 110 ° C. and acid numbers of 5 to 200 mg KOH / g. The dropping point is determined, as in the case of the oxidized polyethylene waxes, in accordance with DIN 51801 or ASTM D 566.
  • the mixtures added according to the invention to improve the flowability of mineral oils and mineral oil distillates consist of two or three components. They always contain ethylene-vinyl acetate copolymers and also oxidized polyethylene waxes or oxidized ethylene-vinyl acetate copolymers. In a further embodiment, according to the new procedure, ethylene-vinyl acetate copolymer is used together with oxidized polyethylene wax and oxidized ethylene-vinyl acetate copolymer.
  • the weight ratio of ethylene-vinyl acetate copolymer to oxidized polyethylene wax and / or oxidized ethylene-vinyl acetate copolymer is 1000: 1 to 1:10. Mixtures are preferred, the copolymer to oxidized wax and / or oxidized copolymer in a weight ratio of 100: 1 to 1: 5 included.
  • mineral oils is understood here in particular to mean crude oils and distillation residues such as heavy heating oil.
  • Mineral oil distillates are hydrocarbon fractions with a boiling temperature between approximately 150 and 400 ° C. These include, for example, petroleum, light heating oils and diesel fuel. Middle distillates such as heating oil EL and diesel fuel are of particular importance.
  • the mixture of the various polymers is added to mineral oils or the mineral oil distillates in the form of solutions which contain 20 to 70% by weight (based on the solution) of the polymers.
  • Suitable solvents are aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions. Kerosene is particularly suitable.
  • the amount of polymer based on mineral oil or mineral oil fractions 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, e.g. with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors and additives to lower the cloud point.
  • additives e.g. with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors and additives to lower the cloud point.
  • Examples 1 to 14 relate to the process according to the invention.
  • Examples 15 and 16 report results of comparative experiments which are obtained using known flow improvers based on an ethylene-vinyl acetate copolymer alone and together with beeswax as the second component.
  • the vinyl acetate content in the polymers A 1 and A 2 is determined by the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask to 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 / KJO 3 solution and the iodine released is titrated with Na 2 S 2 0a solution.
  • Table 2 shows the composition of the polymer mixtures which are used in the middle distillates Mi to M 4 as flow improvers.
  • the polymer mixtures are used as a solution in kerosene (50% by weight of polymer, based on the solution).
  • Table 3 contains information on the effectiveness of the process according to the invention for improving the flowability of mineral oils and mineral oil distillates.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)

Claims (8)

1. Procédé pour l'amélioration de la fluidité des huiles minérales et distillats d'huiles minérales, caractérisé en ce que l'on ajoute aux huiles minérales ou aux distillats d'huiles minérales des mélanges d'un copolymère éthylène-acétate de vinyle et d'une cire de polyéthylène oxydée et/ou d'un copolymère éthylène-acétate de vinyle oxydé.
2. Procédé selon la revendication 1, caractérisé en ce que le copolymère éthylène-acétate de vinyle contient 17 à 70 parties en poids d'acétate de vinyle, de préférence 33 à 54 parties en poids, pour 100 parties en poids d'éthylène, il a une viscosité mesurée à 140°C de 100 à 5 000 mPa.s, de préférence de 200 à 1 500 mPa.s et présente dans les chaînes latérales 1 à 10 groupes CH3, de préférence 2 à 7 groupes CH3, qui ne proviennent pas du reste acétate de l'acétate de vinyle, pour chaque 100 groupes CH2.
3. Procédé selon la revendication 1, caractérisé en ce que la cire de polyéthylène oxydée possède une masse molaire de 500 à 10 000 g.mol-1, un point de fusion de 85 à 135°C, un point de goutte de 95 à 135°C, de préférence 100 à 120°C, une densité de 0,94 à 1,00 g/cm3 et un indice d'acide de 5 à 60 mg de KOH/g, de préférence 8 à 30 mg de KOH/g.
4. Procédé selon la revendication 1, caractérisé en ce que le copolymère éthylène-acétate de vinyle oxydé a un point de goutte de 80 à 110°C et un indice d'acide de 5 à 200 mg de KOH/g.
5. Procédé selon la revendication 1, caractérisé en ce que le rapport pondéral du copolymère éthylène-acétate de vinyle à la cire de polyéthylène oxydée et/ou au copolymère éthylène-acétate de vinyle oxydé est de 1 000:1 à 1:10 et de préférence de 100:1 à 1:5.
6. Huile minérale ou distillat d'huile minérale d'écoulement amélioré, caractérisé(e) en ce qu'il ou elle contient 0,001 à 2% en poids, de préférence 0,005 à 0,5% en poids (par rapport au poids de l'huile minérale ou du distillat d'huile minérale) d'un mélange de copolymère éthylène-acétate de vinyle et d'une cire de polyéthylène oxydée et/ou d'un copolymère éthylène-acétate de vinyle oxydé.
7. Huile minérale ou distillat d'huile minérale selon la revendication 6, caractérisé(e) en ce que,
- le copolymère éthylène-acétate de vinyle contient 17 à 70% en poids d'acétate de vinyle, de préférence 33 à 54% en poids, pour chaque 100 parties en poids d'éthylène, il possède une viscosité à 140°C de 100 à 5 000 mPa.s, de préférence 200 à 1 500 mPa.s et présente dans les chaînes latérales 1 à 10 groupes CHs, de préférence 2 à 7 groupes CHa, qui ne proviennent pas du reste acétate de l'acétate de vinyle, pour chaque 100 groupes CH2,
- la cire de polyéthylène oxydée possède une masse molaire de 500 à 10 000 g.mol-1, un point de fusion de 85 à 135°C, un point de goutte de 95 à 135°C, de préférence 100 à 120°C, une densité de 0,94 à 1,00 g/cm3 et un indice d'acide de 5 à 60 mg de KOH/g, de préférence 8 à 30 mg de KOH/g et
- le copolymère éthylène-acétate de vinyle oxydé possède un point de goutte de 80 à 110°C et un indice d'acide de 5 à 200 mg de KOH/g.
8. Huile minérale ou distillat d'huile minérale selon la revendication 6 ou 7, caractérisé(e) en ce que le rapport pondéral du copolymère éthylène-acétate de vinyle à la cire de polyéthylène oxydée et/ou au copolymère éthylène-acétate de vinyle oxydé est de 1 000:1 à 1:10, de préférence de 100:1 à 1:5.
EP87108559A 1986-06-26 1987-06-13 Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales Expired - Lifetime EP0251002B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87108559T ATE58749T1 (de) 1986-06-26 1987-06-13 Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3621395 1986-06-26
DE19863621395 DE3621395A1 (de) 1986-06-26 1986-06-26 Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten

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EP0251002A1 EP0251002A1 (fr) 1988-01-07
EP0251002B1 true EP0251002B1 (fr) 1990-11-28

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EP87108559A Expired - Lifetime EP0251002B1 (fr) 1986-06-26 1987-06-13 Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales

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EP (1) EP0251002B1 (fr)
AT (1) ATE58749T1 (fr)
DE (2) DE3621395A1 (fr)
ES (1) ES2019901B3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3921279A1 (de) * 1989-06-29 1991-01-03 Hoechst Ag Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
EA011358B1 (ru) * 2003-10-22 2009-02-27 Лейна Полимер Гмбх Композиция минерального нефтетоплива, содержащая смесь присадок, способ ее получения и ее применение

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2875029A (en) * 1953-05-21 1959-02-24 Phillips Petroleum Co Stabilized liquid fuel
US3250599A (en) * 1962-12-03 1966-05-10 Sinclair Research Inc Fuels of improved low temperature pumpability
US3374073A (en) * 1964-06-23 1968-03-19 Lubrizol Corp Oxidized, degraded interpolymer of ethylene and propylene and fuel composition containing the same
US3454379A (en) * 1964-10-23 1969-07-08 Sinclair Research Inc Hydrocarbon oil composition having improved low temperature pumpability
NO121523B (fr) * 1964-12-11 1971-03-08 Exxon Co
US3388977A (en) * 1965-01-06 1968-06-18 Exxon Research Engineering Co Pour point 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
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
US4019878A (en) * 1974-12-17 1977-04-26 Exxon Research And Engineering Company Additive combination for cold flow improvement of middle distillate fuel oil
DE2944375A1 (de) * 1979-11-02 1981-05-14 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von oxidationsprodukten von ethylencopolymerisaten
DE3501384A1 (de) * 1985-01-17 1986-07-17 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten

Also Published As

Publication number Publication date
ES2019901B3 (es) 1991-07-16
ATE58749T1 (de) 1990-12-15
DE3766426D1 (de) 1991-01-10
DE3621395A1 (de) 1988-01-28
EP0251002A1 (fr) 1988-01-07

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