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EP0258572B1 - 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
EP0258572B1
EP0258572B1 EP87109734A EP87109734A EP0258572B1 EP 0258572 B1 EP0258572 B1 EP 0258572B1 EP 87109734 A EP87109734 A EP 87109734A EP 87109734 A EP87109734 A EP 87109734A EP 0258572 B1 EP0258572 B1 EP 0258572B1
Authority
EP
European Patent Office
Prior art keywords
vinyl acetate
ethylene
mineral oil
weight
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
EP87109734A
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German (de)
English (en)
Other versions
EP0258572A1 (fr
Inventor
Wolfgang Dr. Dipl.-Chem. Payer
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.)
Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
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Priority to AT87109734T priority Critical patent/ATE64749T1/de
Publication of EP0258572A1 publication Critical patent/EP0258572A1/fr
Application granted granted Critical
Publication of EP0258572B1 publication Critical patent/EP0258572B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • C10L1/146—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, 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
    • C10L1/16—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0391—Affecting flow by the addition of material or energy

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-diisobutylene terpolymer and an oxidized polyethylene wax and / or 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 ability of crude oil production and transport facilities to function until their complete failure are impaired. 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, for example, in the DE-PS 19 14 756 described. 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 26 39 672 Al describes mixtures of polymers with an ethylene skeleton and copolymers of C2 to C50 olefins, which can lead to a synergistic improvement in the flow properties of distillate hydrocarbon oils in the cold.
  • the object was therefore to find additives which have an even greater range of uses than the known flow improvers. They are also intended to increase the flowability of oils in which the known additives have little or no effect.
  • 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-diisobutylene terpolymer and an oxidized ethylene wax and / or an oxidized polyethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.
  • ethylene-vinyl acetate-diisobutylene terpolymers in combination with oxidized polyethylene waxes and / or oxidized ethylene-vinyl acetate copolymers effectively suppress the separation of paraffins from mineral oils and mineral oil distillates.
  • the additives consisting of certain polymers thus counteract an increase in the viscosity of the hydrocarbon mixtures as temperatures drop and lower the pour point.
  • the new processes have proven themselves to improve the flowability of mineral oils and their distillation products, regardless of their qualitative and quantitative composition.
  • the ethylene-vinyl acetate-diisobutylene terpolymers used according to the invention contain 25 to 78 parts by weight of vinyl acetate and 0.5 to 45 parts by weight of diisobutylene per 100 parts by weight of ethylene. Terpolymers with 30 to 55 parts by weight of vinyl acetate and 1.0 to 27.5 parts by weight of diisobutylene per 100 parts by weight of ethylene have proven particularly useful.
  • the average molecular weight of the terpolymers measured by vapor pressure osmometry is 500 to 10,000 g.mol ⁇ 1, preferably 1000 to 5000 g.mol ⁇ 1 and in particular 1500 to 3500 g.mol ⁇ 1.
  • Each 100 CH2 groups have 6 to 20 and preferably 7 to 15 CH3 groups in the side chains, which do not result from the acetate residue of the vinyl acetate.
  • the number of CH3 groups is determined by H-NMR spectroscopy.
  • the production of the ethylene-vinyl acetate-diisobutylene terpolymers is known. It can e.g. by polymerization of the monomer mixture at pressures above 50 MPa and temperatures from 150 to 350 ° C in the presence of oxygen or radical initiators in autoclaves or tubular reactors.
  • Diisobutylene is a mixture consisting essentially of 2,4,4-trimethylpentene (1) and 2,4,4-trimethylpentene (2). It is formed during the dimerization of isobutylene (2-methylpropene) with acidic catalysts (eg ion exchangers).
  • oxidized polyethylene waxes is understood to mean products which are obtained when air is used to treat linear or branched polyethylene wax melts. 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 / cm3 determined according to 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 e.g. described in DE 29 44 375 A1. 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 acid number is measured in accordance with DIN 53402 or ASTM D 1386.
  • 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-diisobutylene terpolymers and also oxidized polyethylene waxes or oxidized ethylene-vinyl acetate copolymers. In a further embodiment, according to the new procedure, ethylene-vinyl acetate-diisobutylene terpolymer is used together with oxidized polyethylene wax and oxidized ethylene-vinyl acetate copolymer.
  • the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to oxidized polyethylene wax and / or oxidized ethylene-vinyl acetate copolymer is 1000: 1 to 1:10. Mixtures are preferred, the terpolymer to oxidized wax and / or oxidized copolymer in a weight ratio of 100: 1 to 1: 5 included.
  • the process according to the invention improves both the flowability of mineral oils and of mineral oil distillates.
  • 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. Aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, are suitable as solvents. 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 5, 7 and 8 relate to the process according to the invention.
  • example 6 the results of comparative tests are reported which are obtained when an ethylene-vinyl acetate-diisobutylene terpolymer is used as a diluent improver.
  • 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 to 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The resulting acetic acid is reacted with a NaJ / KJO3 solution and the iodine released is titrated with Na2S2O3 solution. The diisobutylene content in the polymer is determined by 13 C-NMR spectroscopy.
  • Table 2 summarizes the results of the investigations, which show 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  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 distillats d'huiles minérales des mélanges d'un terpolymère éthylène-acétate de vinyle-diisobutylène et d'une cire de polyéthylène oxydée et/ou d'un copolymère polyéthylène-acétate de vinyle oxydé.
  2. Procédé selon la revendication 1, caractérisé en ce que le terpolymère éthylène-acétate de vinyle-diisobutylène contient 25 à 78 parties en poids d'acétate de vinyle, en particulier 30 à 55 parties en poids, et 0,5 à 45 parties en poids de diisobutylène, en particulier 1,0 à 27,5 parties en poids, pour 100 parties en poids d'éthylène.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la masse moléculaire moyenne du terpolymère (mesurée par osmométrie de tension de vapeur) est de 500 à 10 000 g.mol⁻¹, de préférence de 1 000 à 5 000 g.mol⁻¹ et en particulier de 1 500 à 3 500 g.mol⁻¹.
  4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que le terpolymère présente, pour 100 groupes CH₂, 6 à 20 et de préférence 7 à 15 groupes CH₃ dans les chaînes latérales, qui ne proviennent pas du reste acétate de l'acétate de vinyle.
  5. Procédé selon la revendication 1, caractérisé en ce que la cire de polyéthylène oxydée a un point de fusion de 85 à 135°C, un point de goutte de 95 à 135°C, en particulier de 100 à 120°C, une densité de 0,94 à 1,00 g/cm³ , un indice d'acide de 5 à 60 mg de KOH/g, en particulier de 8 à 30 mg de KOH/g et une masse moléculaire moyenne de 500 à 10 000 g.mol⁻¹.
  6. 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.
  7. Procédé selon la revendication 1, caractérisé en ce que le rapport pondéral du terpolymère éthylène-acétate de vinyle-diisobutylène 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.
  8. Huile minérale, ou distillat d'huile minérale, ayant une fluidité améliorée, caractérisée en ce qu'elle ou il contient de 0,001 à 2 % en poids, de préférence de 0,005 à 0,5 % en poids (par rapport au poids de l'huile minérale ou du distillat d'huile minérale) d'un mélange d'un terpolymère éthylène-acétate de vinyle-diisobutylène et d'une cire de polyéthylène oxydée et/ou d'un copolymère éthylène-acétate de vinyle oxydé.
  9. Huile minérale, ou distillat d'huile minérale, selon la revendication 8, caractérisée en ce que
    - le terpolymère éthylène-acétate de vinyle-diisobutylène contient 25 à 78 parties en poids d'acétate de vinyle, en particulier 30 à 55 parties en poids, et 0,5 à 45 parties en poids de diisobutylène, en particulier 1,0 à 27,5 parties en poids pour 100 parties en poids d'éthylène, il a une masse moléculaire moyenne (mesurée par osmométrie de tension de vapeur) de 500 à 10 000 g.mol⁻¹, de préférence de 1 000 à 5 000 g.mol⁻¹ et en particulier de 1 500 à 3 500 g.mol⁻¹, et il présente, pour 100 groupes CH₂, 6 à 20 et de préférence 7 à 15 groupes CH₃ dans les chaînes latérales, qui ne proviennent pas du reste acétate de l'acétate de vinyle,
    - la cire de polyéthylène oxydée a un point de fusion de 85 à 135°C, un point de goutte de 95 à 135°C, en particulier de 100 à 120°C, une densité de 0,94 à 1,00 g/cm³, un indice d'acide de 5 à 60 mg de KOH/g, en particulier de 8 à 30 mg de KOH/g et une masse moléculaire moyenne de 500 à 10 000 g.mol⁻¹ , et
    - 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.
  10. Huile minérale, ou distillat d'huile minérale, selon la revendication 8 ou 9, caractérisée en ce que le rapport pondéral du terpolymère-éthylène-acétate de vinyle-diisobutylène à la cire de polyéthylène oxydée et/ou au copolymère-éthylène-acétae de vinyle oxydé est de 1 000 : 1 à 1 : 10, de préférence de 100 : 1 à 1 : 5.
EP87109734A 1986-07-17 1987-07-07 Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales Expired - Lifetime EP0258572B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87109734T ATE64749T1 (de) 1986-07-17 1987-07-07 Verfahren zur verbesserung der fliessfaehigkeit v. mineraloelen u. mineraloeldestillaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863624147 DE3624147A1 (de) 1986-07-17 1986-07-17 Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
DE3624147 1986-07-17

Publications (2)

Publication Number Publication Date
EP0258572A1 EP0258572A1 (fr) 1988-03-09
EP0258572B1 true EP0258572B1 (fr) 1991-06-26

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EP87109734A Expired - Lifetime EP0258572B1 (fr) 1986-07-17 1987-07-07 Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales

Country Status (6)

Country Link
US (1) US4862908A (fr)
EP (1) EP0258572B1 (fr)
AT (1) ATE64749T1 (fr)
CA (1) CA1276444C (fr)
DE (2) DE3624147A1 (fr)
ES (1) ES2024459B3 (fr)

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Also Published As

Publication number Publication date
ATE64749T1 (de) 1991-07-15
ES2024459B3 (es) 1992-03-01
US4862908A (en) 1989-09-05
DE3624147A1 (de) 1988-01-21
CA1276444C (fr) 1990-11-20
EP0258572A1 (fr) 1988-03-09
DE3771016D1 (de) 1991-08-01

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