EP0938534B1 - Utilisation d'un additif pour ameliorer les proprietes d'huiles lourdes - Google Patents

Utilisation d'un additif pour ameliorer les proprietes d'huiles lourdes Download PDF

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Publication number
EP0938534B1
EP0938534B1 EP97912206A EP97912206A EP0938534B1 EP 0938534 B1 EP0938534 B1 EP 0938534B1 EP 97912206 A EP97912206 A EP 97912206A EP 97912206 A EP97912206 A EP 97912206A EP 0938534 B1 EP0938534 B1 EP 0938534B1
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Prior art keywords
acid
component
weight
carbon atoms
additive
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EP97912206A
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German (de)
French (fr)
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EP0938534A1 (en
Inventor
Günther Hertel
Michael Feustel
Hakan Byström
Geoffrey Richards
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Clariant Produkte Deutschland GmbH
BYCOSIN AB
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Clariant GmbH
BYCOSIN AB
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    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1885—Carboxylic acids; metal salts thereof resin acid
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
    • 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
    • C10L1/238—Macromolecular compounds obtained otherwise than 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only

Definitions

  • the invention relates to the use of an additive to improve the Properties of heavy oils and heavy oils with this additive.
  • Heavy oils are used in the processing of petroleum (Crude oils) preserved and are residues of Processing processes such as distillation under Atmospheric pressure or vacuum, thermal or catalytic cracking and the like. Chemically speaking are these residual fuels or Residual fuels (bunker C oils) essentially from paraffinic, naphthenic and aromatic Hydrocarbons of partially high molecular weight Structure.
  • the high molecular components, too Called asphaltenes are not solved, but in a more or less dispersed form from what several problems result.
  • Heavy oils especially in the form of heavy heating oils (Marine Fuel Oils) and mixtures of heavy Heating oils and heavy distillates (Inter Fuel Oils) are used in large quantities mainly as fuel Industrial plants and power plants and as fuel for slower running internal combustion engines, in particular Marine engines.
  • Marine Fuel Oils and mixtures of heavy Heating oils and heavy distillates
  • Inter Fuel Oils are used in large quantities mainly as fuel Industrial plants and power plants and as fuel for slower running internal combustion engines, in particular Marine engines.
  • FR-A-2 172 797 describes basic iron salts of organic acids and in FR-A-2 632 966 a mixture of Iron hydroxide and a basic calcium soap as Tools to improve the combustion of Heavy oils described.
  • US-A-4,129,589 highly basic and oil soluble magnesium salts from Sulphonic acids recommended as oil additives.
  • one Document EP-A-476 196 is a mixture consisting of essentially from (1) at least one oil-soluble Manganese carbonyl compound, (2) at least one oil-soluble neutral or basic alkali or Alkaline earth metal salt from an organic Acid component and (3) at least one oil-soluble Dispersants from the group of succinimides described as an oil additive.
  • US-A-5 421 993 wherein oxalkylated fatty amines and Fatty amine derivatives as corrosion inhibitors, Demulsifiers and pour point depressants for crude oils are described.
  • the amine compounds of formula (VI) and their Manufacturing are in the aforementioned US-A-5 421 993 described in detail here is involved. They are made by oxalkylation of Amines of the formulas (II) to (V) given first with Ethylene oxide and then with propylene oxide with the addition of Obtain bases such as alkali metal hydroxides. The implementation takes place in stages at a temperature of preferably 100 to 160 ° C. The amount of wagered The catalyst / base is generally 0.5 to 3.0% by weight, based on the starting amine used.
  • Preferred metals in the metal salt compound of the Component b) are the alkali or alkaline earth metals (first and second main group of the periodic table), Copper or silver (first subgroup), zinc or Cadmium (second sub-group), titanium or zircon (fourth Subgroup), molybdenum, chromium or tungsten (sixth Subgroup), iron, cobalt or nickel (eighth Subgroup) and lanthanum, cerium or ytterbium (Lanthanide group).
  • Metals are particularly preferred the alkaline earth metals such as barium, beryllium, calcium or Magnesium, copper, zinc, zircon, molybdenum, iron, Nickel, cerium or ytterbium.
  • Preferred acids in the metal salt compound of the Component b) are aliphatic carboxylic acids 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms.
  • the aliphatic rest can be straight or be branched, saturated or unsaturated.
  • the aliphatic carboxylic acids are preferably fatty acids with 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms.
  • the aliphatic carboxylic acids and Fatty acids can be synthetic or natural and as such or as a mixture of two or more acids are present.
  • octanoic acid caprylic acid
  • decanoic acid Capric acid
  • dodecanoic acid lauric acid
  • Tetradecanoic acid myristic acid
  • hexadecanoic acid Palmitic acid
  • octadecanoic acid stearic acid
  • Eicosanoic acid arachic acid
  • docosanoic acid behenic acid
  • Dodecenoic acid laauroleic acid
  • tetradecenoic acid Myristoleic acid
  • hexadecenoic acid palmitoleic acid
  • Octadecenoic acid oleic acid
  • 12-oxy-octadecenoic acid Rosin
  • octadecadienoic acid octadecadienoic acid
  • Octadecatrienoic acid lainolenic acid
  • coconut fatty acid Tallow fatty acid, palm kernel fatty acid and the like.
  • dimeric fatty acids are also preferred acid components. These dimeric fatty acids correspond to the following formula (VII) HOOC-R 2 -COOH where R 2 is a divalent hydrocarbon radical with 34 C atoms (R 2 thus represents the radical containing 34 C atoms which is formed when an unsaturated fatty acid with 18 C atoms is dimerized to form a dicarboxylic acid with a total of 36 C atoms).
  • dimerization means the union of two identical molecules to form a new molecule, the dimer, by means of an addition reaction.
  • the dimerization of C 18 fatty acids is generally carried out at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst.
  • the dicarboxylic acid obtained corresponds to the formula VII given, where R 2 is the divalent linkage formed in the dimerization of the C 18 fatty acid, which bears the two -COOH groups and has 34 C atoms.
  • R 2 is preferably an acyclic (aliphatic) or a mono- or bicyclic (cycloaliphatic) radical with 34 C atoms.
  • the acyclic radical is usually a branched (substituted) and mono- to trisaturated alkyl radical with 34 carbon atoms.
  • the cycloaliphatic radical generally also has 1 to 3 double bonds.
  • the preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of the formula VII with structurally different R 2 radicals.
  • the dicarboxylic acid mixture often has a more or less large content of trimeric fatty acids, which were formed during the dimerization and were not removed during the working up of the product by distillation. Similar mixtures are also obtained from natural products, for example in the manufacture of rosin from pine extract.
  • some dimeric fatty acids are given in terms of formula, the hydrocarbon radical bearing the two -COOH groups being an acyclic, monocyclic or bicyclic radical:
  • dimeric fatty acids described are commercially available under the name "dimerized fatty acids" or “Dimer fatty acids” are available and can, as above already mentioned, a more or less high proportion of contain trimerized fatty acids.
  • Preferred acids in the metal salt compound of the Component b) are also aliphatic or aromatic Sulfonic acids with 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms, in aliphatic or aromatic radical.
  • the aliphatic The rest can be straight or branched, saturated or be unsaturated.
  • the aromatic sulfonic acid is preferably a benzenesulfonic acid with an alkyl or Alkenyl radical with 12 to 30 carbon atoms.
  • Metal soaps are particularly preferred.
  • organic metal salts can according to the state of the art Techniques described methods can be produced. there be particularly to the above Documents FR-A-2 172 797, FR-A-2 632 966, US-A-4 129 589 and EP-A-476 196, which are here be included.
  • organic metal salts are said to be oil-soluble or at least be oil dispersible. It is also a neutral or basic product, the latter is preferred.
  • basic denotes as is known such metal salts in which the metal in a stoichiometrically larger amount than the organic one Acid radical is present.
  • the invention have basic metal salt products to be used accordingly a pH of generally 7.5 to 12, preferably from 8 to 10.
  • the additive used according to the invention is produced by mixing components a) and b) together, optionally using a solution or Dispersant.
  • Suitable such means are lower or higher alcohols such as ethanol, isopropanol, Butanol, decanol, dodecanol and the like, lower or higher glycols and their mono- or dialkyl ethers such as ethylene glycol, propylene glycol, diethylene glycol, Tetraethylene glycol, tetrapropylene glycol and the like, low to medium high boiling aliphatic, aromatic or cycloaliphatic hydrocarbons such as toluene, xylene, naphtha and the like, light to medium heavy mineral oils, oil distillates, natural or synthetic oils and derivatives thereof and mixtures of two or more of these solvents.
  • the Bringing the two components together, amine compound and metal salt compound generally takes place at Atmospheric pressure and a temperature of 15 to 100 ° C, preferably 20 to 70 ° C.
  • the heavy oils are marked by a content of the additive described.
  • the effective amount of additive in heavy oil can vary widely Limits vary. Generally the oil contains 2 to 2000 ppm additive, preferably 100 to 1000 ppm.
  • the additive used according to the invention and the heavy oils with this additive have a particularly desirable one Property profile on, and this should be mostly on an unexpectedly high synergism of those used according to the invention Combination of components a) and b) are based. So lies the additive dissolved or highly distributed in the oil. Also in Oils with a high content of asphaltenes and / or other higher molecular compounds are all of these insoluble parts well emulsified or dispersed. The the same applies in the case of sludge, so that too Sludge formation largely eliminated or at least is significantly reduced.
  • the additive used according to the invention is also a highly effective combustion improver. It ensures the complete combustion of heavy Oil while reducing soot formation.
  • the heavy oils according to the invention thus fulfill the requirements mentioned in a surprising high degree.
  • improved storage stability reduced separation of insoluble components
  • improved pumpability due to low viscosity longer service life of the filter systems
  • improved Injection behavior at the combustion devices what additionally contributes to the optimization of the combustion
  • increased corrosion protection for all facilities the good corrosion inhibition of the additive are therefore, above all as fuel for industrial plants and power plants used and also as a fuel for marine engines.
  • the fatty acid used to produce product b 1 is a distilled fatty acid consisting of a mixture (blend) of distilled talc oil fatty acid and resin acid with a molecular weight of about 300 g / mol. Approach: FeCl 3 0.85 l Density 1.48 g / cm 3 NH 3 0.785 l Density 0.91 g / cm 3 fatty acid 0.22 l Density 0.94 g / cm 3 water 0.20 l Petroleum distillate 0.80 l Density 0.82 g / cm 3
  • the 0.85 l FeCl 3 , 0.22 l fatty acid, 0.20 l water and 0.80 l petroleum distillate are mixed together at room temperature (15 to 30 ° C).
  • the 0.785 l of NH 3 are slowly introduced into this mixture with stirring (exothermic reaction).
  • the mixture is heated to 80 to 90 ° C. with stirring, an aqueous and an organic phase being formed.
  • the phase formation can be completed by adding more petroleum distillate.
  • the two phases are separated from one another (decanted), whereupon the organic phase is still centrifuged to remove residual water.
  • the organic phase contains the desired iron carboxylate compound.
  • the fatty acid used to produce product b 2 is an alkylbenzenesulfonic acid with a molecular weight of approximately 322 g / mol.
  • Comparative Examples 1 to 3 the compounds a 1 , a 3 and b 1 are each used alone.
  • the three test solutions are subjected to the same test procedure as the examples according to the invention. Result: All test solutions do not meet the asphaltene dispersibility test or the combustibility improvement test.
  • the additives used therefore have a unexpectedly high effectiveness regarding dispersion of Asphaltenes in heavy oils and also with regard to combustion of heavy oils; this should come from a surprisingly high Synergism of additive components a) and b) result. Because of the beneficial effects of The oils show new additives all those properties that are essential for use in industrial plants, power plants and heavy Ship engines are particularly desired.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Description

Die Erfindung betrifft die Verwendung eines Additivs zur Verbesserung der Eigenschaften von schweren Ölen und schwere Öle mit diesem Additiv.The invention relates to the use of an additive to improve the Properties of heavy oils and heavy oils with this additive.

Schwere Öle werden bei der Verarbeitung von Erdölen (Rohölen) erhalten und sind Rückstände von Verarbeitungsprozessen wie Destillation unter Atmosphärendruck oder Vakuum, thermische oder katalytische Crackung und dergleichen. Chemisch gesehen bestehen diese Rückstandsbrennstoffe oder Rückstandstreibstoffe (Bunker-C-Öle) im wesentlichen aus paraffinischen, naphthenischen und aromatischen Kohlenwasserstoffen von teilweise hochmolekularer Struktur. Die hochmolekularen Komponenten, auch Asphaltene genannt, liegen nicht gelöst, sondern in einer mehr oder weniger dispergierten Form vor, woraus mehrere Probleme resultieren. So können Asphaltene und ebenso andere schwer oder unlösliche Verbindungen (zum Beispiel Sauerstoff-, Stickstoff- und Schwefelverbindungen) und Alterungsprodukte in Abwesenheit wirksamer Dispergatoren aus der Ölphase ausscheiden unter Bildung eines äußerst unerwünschten Zweiphasensystems. In Gegenwart von Wasser oder auch nur Feuchtigkeit kann es ferner zur Schlammbildung kommen. All diese höher molekularen Verbindungen und Anteile im Schweröl beeinträchtigen darüber hinaus den Vorgang der Verbrennung des Öles, zum Beispiel durch verstärkte Rußbildung. Heavy oils are used in the processing of petroleum (Crude oils) preserved and are residues of Processing processes such as distillation under Atmospheric pressure or vacuum, thermal or catalytic cracking and the like. Chemically speaking are these residual fuels or Residual fuels (bunker C oils) essentially from paraffinic, naphthenic and aromatic Hydrocarbons of partially high molecular weight Structure. The high molecular components, too Called asphaltenes are not solved, but in a more or less dispersed form from what several problems result. So asphaltenes and also other difficult or insoluble compounds (to Example oxygen, nitrogen and Sulfur compounds) and aging products in Absence of effective dispersants from the oil phase Eliminate to form an extremely undesirable Two-phase system. In the presence of water or just Moisture can also lead to sludge formation. All of these higher molecular compounds and proportions in the Heavy oil also affect the process of Combustion of the oil, for example through increased Soot formation.

Schwere Öle, insbesondere in Form von schweren Heizölen (Marine Fuel Oils) und von Mischungen von schweren Heizölen und schweren Destillaten (Inter Fuel Oils) werden in großen Mengen vor allem als Brennstoff in Industrieanlagen und Kraftwerken und als Treibstoff für langsamer laufende Verbrennungsmotoren, insbesondere Schiffsmotoren, eingesetzt. Im Stand der Technik sind deshalb bereits zahlreiche Vorschläge für Additive gemacht worden, womit die beschriebenen nachteiligen Eigenschaften der schweren Brenn- und Treibstofföle, das sind insbesondere die Zweiphasenbildung durch Asphaltene und andere höher molekulare Anteile," die Schlammbildung und die Beeinträchtigung der Verbrennung, ausgeschaltet werden sollten.Heavy oils, especially in the form of heavy heating oils (Marine Fuel Oils) and mixtures of heavy Heating oils and heavy distillates (Inter Fuel Oils) are used in large quantities mainly as fuel Industrial plants and power plants and as fuel for slower running internal combustion engines, in particular Marine engines. Are in the prior art therefore already numerous suggestions for additives was made, with which the described disadvantageous Properties of heavy fuel and fuel oils, the are in particular the two-phase formation by asphaltenes and other higher molecular fractions, "sludge formation and the impairment of combustion, turned off should be.

So werden in FR-A-2 172 797 basische Eisensalze von organischen Säuren und in FR-A-2 632 966 ein Gemisch von Eisenhydroxid und einer basischen Calciumseife als Hilfsmittel zur Verbesserung der Verbrennung von Schwerölen beschrieben. In US-A-4 129 589 werden hochbasische und öllösliche Magnesiumsalze von Sulfonsäuren als Öladditive empfohlen. In der neueren Druckschrift EP-A-476 196 wird ein Gemisch bestehend im wesentlichen aus (1) mindestens einer öllöslichen Mangancarbonyl-Verbindung, (2) mindestens einem öllöslichen neutralen oder basischen Alkali- oder Erdalkalimetallsalz von einer organischen Säurekomponente und (3) mindestens einem öllöslichen Dispergiermittel aus der Gruppe der Bernsteinsäureimide als Öladditiv beschrieben. Erwähnt sei auch noch US-A-5 421 993, worin oxalkylierte Fettamine und Fettaminderivate als Korrosionsinhibitoren, Demulgatoren und Stockpunktserniedriger für Rohöle beschrieben sind. For example, FR-A-2 172 797 describes basic iron salts of organic acids and in FR-A-2 632 966 a mixture of Iron hydroxide and a basic calcium soap as Tools to improve the combustion of Heavy oils described. In US-A-4,129,589 highly basic and oil soluble magnesium salts from Sulphonic acids recommended as oil additives. In the newer one Document EP-A-476 196 is a mixture consisting of essentially from (1) at least one oil-soluble Manganese carbonyl compound, (2) at least one oil-soluble neutral or basic alkali or Alkaline earth metal salt from an organic Acid component and (3) at least one oil-soluble Dispersants from the group of succinimides described as an oil additive. It should also be mentioned US-A-5 421 993, wherein oxalkylated fatty amines and Fatty amine derivatives as corrosion inhibitors, Demulsifiers and pour point depressants for crude oils are described.

Es wurde nun gefunden, daß die Kombination von oxalkylierten Fettaminverbindungen und organischen Metallsalzen ein besonders wirksames Additiv für schwere Öle ist, insbesondere hinsichtlich Emulgierung und/oder Dispergierung von Asphaltenen, Schlamm und dergleichen und auch hinsichtlich Verbesserung der Ölverbrennung.It has now been found that the combination of oxalkylated fatty amine compounds and organic Metal salts a particularly effective additive for heavy Is oils, especially with regard to emulsification and / or Dispersion of asphaltenes, mud and the like and also in terms of improving oil combustion.

Das erfindungsgemäße Verwendete Additiv besteht im wesentlichen aus

  • a) 1 bis 99 Gew.-%, vorzugsweise 20 bis 80 Gew.-% und insbesondere 40 bis 60 Gew.-%, von mindestens einer Aminverbindung der nachstehenden Formel (I)
    Figure 00030001
       worin bedeuten
    n
    1, 2, 3 oder 4,
    A
    einen Rest der Formeln (II) bis (V)
    Figure 00030002
    Figure 00030003
    wobei R ein C6 bis C22-Alkyl ist, vorzugsweise ein C6 bis C18-Alkyl, und m 2, 3 oder 4 ist, vorzugsweise 2 oder 3,
    x
    eine Zahl von 5 bis 120, vorzugsweise 10 bis 80,
    R1
    H, CH3 oder H und CH3, wobei die Oxalkylenreste statistisch oder in Blöcken angeordnet sind, und
  • b) 1 bis 99 Gew.-%, vorzugsweise 20 bis 80 Gew.-% und insbesondere 40 bis 60 Gew.-%, von mindestens einer öllöslichen oder öldispergierbaren, neutralen oder basischen Metallsalzverbindung mit einem Metall der ersten Hauptgruppe des Periodensystems der Elemente, der zweiten Hauptgruppe, der ersten Nebengruppe, der zweiten Nebengruppe, der vierten Nebengruppe, der sechsten Nebengruppe, der achten Nebengruppe oder der Lanthanidengruppe (seltene Erdmetalle) des Periodensystems und einer Carbonsäure, Sulfonsäure, Esterphosphorsäure oder Esterschwefelsäure mit einem Kohlenwasserstoffrest von jeweils 8 bis 40 Kohlenstoffatomen, vorzugsweise 12 bis 30 Kohlenstoffatomen, als Säurekomponente,
    • Gewichtsprozente bezogen auf das Additiv.The additive used according to the invention consists essentially of
  • a) 1 to 99% by weight, preferably 20 to 80% by weight and in particular 40 to 60% by weight, of at least one amine compound of the formula (I) below
    Figure 00030001
    in what mean
    n
    1, 2, 3 or 4,
    A
    a radical of the formulas (II) to (V)
    Figure 00030002
    Figure 00030003
    wherein R is a C 6 to C 22 alkyl, preferably a C 6 to C 18 alkyl, and m is 2, 3 or 4, preferably 2 or 3,
    x
    a number from 5 to 120, preferably 10 to 80,
    R 1
    H, CH 3 or H and CH 3 , the oxalkylene radicals being arranged randomly or in blocks, and
  • b) 1 to 99% by weight, preferably 20 to 80% by weight and in particular 40 to 60% by weight, of at least one oil-soluble or oil-dispersible, neutral or basic metal salt compound with a metal of the first main group of the Periodic Table of the Elements, the second main group, the first subgroup, the second subgroup, the fourth subgroup, the sixth subgroup, the eighth subgroup or the lanthanide group (rare earth metals) of the periodic table and a carboxylic acid, sulfonic acid, ester phosphoric acid or ester sulfuric acid with a hydrocarbon residue of 8 to 40 carbon atoms each , preferably 12 to 30 carbon atoms, as the acid component,
    • Percentages by weight based on the additive.

    Die Komponente a) der erfindungsgemäßen Verwendete Additive ist eine Aminverbindung gemäß Formel (I). Diese oxalkylierten Fettamine und Fettaminderivate werden nach üblichen Oxalkylierungsverfahren hergestellt, indem ein Amin gemäß Rest A in Formel (I) mit x mol Ethylenoxid allein (R1 ist H und der Polyoxalkylenrest besteht aus Ethylenoxideinheiten) oder mit x mol Propylenoxid allein (R1 ist CH3 und der Polyoxalkylenrest besteht aus Propylenoxideinheiten) oder mit x mol Ethylenoxid und Propylenoxid gleichzeitig oder nacheinander
    (R1 ist H und CH3 und der Polyoxalkylenrest besteht aus Ethylenoxid- und Propylenoxideinheiten, die statistisch verteilt beziehungsweise blockweise vorliegen) umgesetzt wird. Die Umsetzung wird im allgemeinen bei einer Temperatur von 100 bis 180 °C gegebenenfalls in Gegenwart eines alkalischen oder sauren Oxalkylierungskatalysators unter Luftausschluß durchgeführt. Bevorzugte Aminverbindungen als Komponente a) entsprechen der nachstehenden Formel (VI)

    Figure 00050001
       worin bedeuten

    n
    1, 2, 3 oder 4,
    A
    einen Rest der oben angegebenen Formeln (II) bis (V) ,
    a
    eine Zahl von 5 bis 30, vorzugsweise 8 bis 20,
    b
    eine Zahl von 5 bis 50, vorzugsweise 10 bis 30, und
    c
    eine Zahl von 0 bis 40, vorzugsweise 0 bis 20.
    Component a) of the additives used according to the invention is an amine compound of the formula (I). These oxyalkylated fatty amines and fatty amine derivatives are prepared by customary oxyalkylation processes, in that an amine according to radical A in formula (I) with x mol ethylene oxide alone (R 1 is H and the polyoxalkylene radical consists of ethylene oxide units) or with x mol propylene oxide alone (R 1 is CH 3 and the polyoxalkylene radical consists of propylene oxide units) or with x mol ethylene oxide and propylene oxide simultaneously or in succession
    (R 1 is H and CH 3 and the polyoxalkylene radical consists of ethylene oxide and propylene oxide units which are randomly distributed or are present in blocks). The reaction is generally carried out at a temperature of 100 to 180 ° C., optionally in the presence of an alkaline or acidic oxyalkylation catalyst, with the exclusion of air. Preferred amine compounds as component a) correspond to the following formula (VI)
    Figure 00050001
    in what mean
    n
    1, 2, 3 or 4,
    A
    a radical of the formulas (II) to (V) given above,
    a
    a number from 5 to 30, preferably 8 to 20,
    b
    a number from 5 to 50, preferably 10 to 30, and
    c
    a number from 0 to 40, preferably 0 to 20.

    Die Aminverbindungen der Formel (VI) und ihre Herstellung sind in der eingangs genannten US-A-5 421 993 ausführlich beschrieben, die hier miteinbezogen wird. Sie werden durch Oxalkylierung von Aminen der angegebenen Formeln (II) bis (V) zuerst mit Ethylenoxid und dann mit Propylenoxid unter Zusatz von Basen wie Alkalimetallhydroxiden erhalten. Die Umsetzung erfolgt in Stufen bei einer Temperatur von vorzugsweise 100 bis 160 °C. Die Menge an eingesetztem Katalysator/Base liegt im allgemeinen bei 0,5 bis 3,0 Gew.-%, bezogen auf das eingesetzte Ausgangsamin. The amine compounds of formula (VI) and their Manufacturing are in the aforementioned US-A-5 421 993 described in detail here is involved. They are made by oxalkylation of Amines of the formulas (II) to (V) given first with Ethylene oxide and then with propylene oxide with the addition of Obtain bases such as alkali metal hydroxides. The implementation takes place in stages at a temperature of preferably 100 to 160 ° C. The amount of wagered The catalyst / base is generally 0.5 to 3.0% by weight, based on the starting amine used.

    Die Molmenge an Ethylenoxid und Propylenoxid pro mol Ausgangsamin entspricht den angegebenen Werten für a und b und den Werten für c. Im einzelnen wird auf die genannte US-A-5 421 993 hingewiesen. In der folgenden Zusammenfassung sind Beispiele für geeignete Aminverbindungen (a1 bis a6) gemäß-Formel (I) als Komponente a) angegeben: Formel (I) Verbindung A R a b c a1 II C14 bis C18-Alkyl ungesättigt 22 33 0 a2 III C14 bis C18-Alkyl ungesättigt 6 9 0 a3 V C14 bis C18-Alkyl ungesättigt 22 33 0 a4 IV C14 bis C18-Alkyl ungesättigt 22 33 0 a5 III C14 bis C18-Alkyl ungesättigt 12 28 25 a6 III C14 bis C18-Alkyl ungesättigt 12 28 15 The molar amount of ethylene oxide and propylene oxide per mol of starting amine corresponds to the values given for a and b and the values for c. Reference is made specifically to the aforementioned US Pat. No. 5,421,993. The following summary gives examples of suitable amine compounds (a 1 to a 6 ) according to formula (I) as component a): Formula (I) connection A R a b c a 1 II C 14 to C 18 alkyl unsaturated 22 33 0 a 2 III C 14 to C 18 alkyl unsaturated 6 9 0 a 3 V C 14 to C 18 alkyl unsaturated 22 33 0 a 4 IV C 14 to C 18 alkyl unsaturated 22 33 0 a 5 III C 14 to C 18 alkyl unsaturated 12th 28 25th a 6 III C 14 to C 18 alkyl unsaturated 12th 28 15

    Bevorzugte Metalle in der Metallsalzverbindung der Komponente b) sind die Alkali- oder Erdalkalimetalle (erste und zweite Hauptgruppe des Periodensystems), Kupfer oder Silber (erste Nebengruppe), Zink oder Cadmium (zweite Nebengruppe), Titan oder Zirkon (vierte Nebengruppe), Molybdän, Chrom oder Wolfram (sechste Nebengruppe), Eisen, Kobalt oder Nickel (achte Nebengruppe) und Lanthan, Cer oder Ytterbium (Lanthanidengruppe). Besonders bevorzugte Metalle sind die Erdalkalimetalle wie Barium, Beryllium, Calcium oder Magnesium, Kupfer, Zink, Zirkon, Molybdän, Eisen, Nickel, Cer oder Ytterbium. Preferred metals in the metal salt compound of the Component b) are the alkali or alkaline earth metals (first and second main group of the periodic table), Copper or silver (first subgroup), zinc or Cadmium (second sub-group), titanium or zircon (fourth Subgroup), molybdenum, chromium or tungsten (sixth Subgroup), iron, cobalt or nickel (eighth Subgroup) and lanthanum, cerium or ytterbium (Lanthanide group). Metals are particularly preferred the alkaline earth metals such as barium, beryllium, calcium or Magnesium, copper, zinc, zircon, molybdenum, iron, Nickel, cerium or ytterbium.

    Bevorzugte Säuren in der Metallsalzverbindung der Komponente b) sind aliphatische Carbonsäuren mit 8 bis 40 Kohlenstoffatomen, vorzugsweise 12 bis 30 Kohlenstoffatomen. Der aliphatische Rest kann gerade oder verzweigt, gesättigt oder ungesättigt sein. Die aliphatischen Carbonsäuren sind vorzugsweise Fettsäuren mit 8 bis 40 Kohlenstoffatomen, vorzugsweise 12 bis 30 Kohlenstoffatomen. Die aliphatischen Carbonsäuren und Fettsäuren können synthetischer oder natürlicher Art sein, und sie können als solche oder als Gemisch von zwei oder mehreren Säuren vorliegen. Als Beispiele seien genannt Octansäure (Caprylsäure), Decansäure (Caprinsäure), Dodecansäure (Laurinsäure), Tetradecansäure (Myristinsäure), Hexadecansäure (Palmitinsäure), Octadecansäure (Stearinsäure), Eicosansäure (Arachinsäure), Docosansäure (Behensäure), Dodecensäure (Lauroleinsäure), Tetradecensäure (Myristoleinsäure), Hexadecensäure (Palmitoleinsäure), Octadecensäure (Ölsäure), 12-Oxy-octadecensäure (Ricinolsäure), Octadecadiensäure (Linolsäure) und Octadecatriensäure (Linolensäure) sowie Cocosfettsäure, Talgfettsäure, Palmkernfettsäure und dergleichen.Preferred acids in the metal salt compound of the Component b) are aliphatic carboxylic acids 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms. The aliphatic rest can be straight or be branched, saturated or unsaturated. The aliphatic carboxylic acids are preferably fatty acids with 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms. The aliphatic carboxylic acids and Fatty acids can be synthetic or natural and as such or as a mixture of two or more acids are present. As examples called octanoic acid (caprylic acid), decanoic acid (Capric acid), dodecanoic acid (lauric acid), Tetradecanoic acid (myristic acid), hexadecanoic acid (Palmitic acid), octadecanoic acid (stearic acid), Eicosanoic acid (arachic acid), docosanoic acid (behenic acid), Dodecenoic acid (lauroleic acid), tetradecenoic acid (Myristoleic acid), hexadecenoic acid (palmitoleic acid), Octadecenoic acid (oleic acid), 12-oxy-octadecenoic acid (Ricinoleic acid), octadecadienoic acid (linoleic acid) and Octadecatrienoic acid (linolenic acid) and coconut fatty acid, Tallow fatty acid, palm kernel fatty acid and the like.

    Neben den genannten (einfachen) Fettsäuren stellen auch dimere Fettsäuren bevorzugte Säurekomponenten dar. Diese dimeren Fettsäuren entsprechen der nachstehenden Formel (VII) HOOC-R2-COOH    worin R2 ein zweiwertiger Kohlenwasserstoffrest mit 34 C-Atomen ist (R2 stellt also den 34 C-Atome enthaltenden Rest dar, der bei der Dimerisation einer ungesättigten Fettsäure mit 18 C-Atomen zu einer Dicarbonsäure mit insgesamt 36 C-Atomen entsteht).In addition to the (simple) fatty acids mentioned, dimeric fatty acids are also preferred acid components. These dimeric fatty acids correspond to the following formula (VII) HOOC-R 2 -COOH where R 2 is a divalent hydrocarbon radical with 34 C atoms (R 2 thus represents the radical containing 34 C atoms which is formed when an unsaturated fatty acid with 18 C atoms is dimerized to form a dicarboxylic acid with a total of 36 C atoms).

    Sie werden bekanntlich durch Dimerisation von ungesättigten C18-Fettsäuren hergestellt, zum Beispiel von Ölsäure, Linolsäure, Linolensäure oder Talgfettsäure (unter Dimerisation versteht man die Vereinigung von zwei identischen Molekülen zu einem neuen Molekül, dem Dimeren, durch Additionsreaktion). Die Dimerisation von C18-Fettsäuren wird in der Regel bei einer Temperatur von 150 bis 250 °C, vorzugsweise 180 bis 230 °C, mit oder ohne Dimerisierungskatalysator durchgeführt. Die erhaltene Dicarbonsäure (das ist die dimere Fettsäure) entspricht der angegebenen Formel VII, wobei R2 das bei der Dimerisation der C18-Fettsäure gebildete zweiwertige Verbindungsglied ist, das die beiden -COOH-Gruppen trägt und 34 C-Atome aufweist. R2 ist vorzugsweise ein acyclischer (aliphatischer) oder ein mono- oder bicyclischer (cycloaliphatischer) Rest mit 34 C-Atomen. Der acyclische Rest ist in der Regel ein verzweigter (substituierter) und ein- bis dreifach ungesättigter Alkylrest mit 34 C-Atomen. Der cycloaliphatische Rest hat im allgemeinen ebenfalls 1 bis 3 Doppelbindungen. Die beschriebenen bevorzugten dimeren Fettsäuren sind im allgemeinen ein Gemisch von zwei oder mehreren Dicarbonsäuren der Formel VII mit strukturell verschiedenen R2-Resten. Das Dicarbonsäuregemisch hat häufig einen mehr oder weniger großen Gehalt von trimeren Fettsäuren, die bei der Dimerisation entstanden und bei der destillativen Aufarbeitung des Produktes nicht entfernt worden sind. Ähnliche Gemische werden auch aus Naturprodukten erhalten, zum Beispiel bei der Kolophonium-Herstellung aus Pinienextrakt. Im folgenden seien einige dimere Fettsäuren formelmäßig angegeben, wobei der die beiden -COOH-Gruppen tragende Kohlenwasserstoffrest ein acyclischer, monocyclischer oder bicyclischer Rest ist:

    Figure 00090001
    Figure 00090002
    Figure 00090003
    As is known, they are produced by dimerization of unsaturated C 18 fatty acids, for example oleic acid, linoleic acid, linolenic acid or tallow fatty acid (dimerization means the union of two identical molecules to form a new molecule, the dimer, by means of an addition reaction). The dimerization of C 18 fatty acids is generally carried out at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst. The dicarboxylic acid obtained (this is the dimeric fatty acid) corresponds to the formula VII given, where R 2 is the divalent linkage formed in the dimerization of the C 18 fatty acid, which bears the two -COOH groups and has 34 C atoms. R 2 is preferably an acyclic (aliphatic) or a mono- or bicyclic (cycloaliphatic) radical with 34 C atoms. The acyclic radical is usually a branched (substituted) and mono- to trisaturated alkyl radical with 34 carbon atoms. The cycloaliphatic radical generally also has 1 to 3 double bonds. The preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of the formula VII with structurally different R 2 radicals. The dicarboxylic acid mixture often has a more or less large content of trimeric fatty acids, which were formed during the dimerization and were not removed during the working up of the product by distillation. Similar mixtures are also obtained from natural products, for example in the manufacture of rosin from pine extract. In the following, some dimeric fatty acids are given in terms of formula, the hydrocarbon radical bearing the two -COOH groups being an acyclic, monocyclic or bicyclic radical:
    Figure 00090001
    Figure 00090002
    Figure 00090003

    Die beschriebenen dimeren Fettsäuren sind im Handel unter der Bezeichnung "dimerisierte Fettsäuren" oder "Dimerfettsäuren" erhältlich sind und können, wie oben bereits erwähnt, einen mehr oder weniger hohen Anteil an trimerisierten Fettsäuren enthalten.The dimeric fatty acids described are commercially available under the name "dimerized fatty acids" or "Dimer fatty acids" are available and can, as above already mentioned, a more or less high proportion of contain trimerized fatty acids.

    Bevorzugte Säuren in der Metallsalzverbindung der Komponente b) sind ferner aliphatische oder aromatische Sulfonsäuren mit 8 bis 40 Kohlenstoffatomen, vorzugsweise 12 bis 30 Kohlenstoffatomen, im aliphatischen oder aromatischen Rest. Der aliphatische Rest kann auch hier gerade oder verzweigt, gesättigt oder ungesättigt sein. Die aromatische Sulfonsäure ist vorzugsweise eine Benzolsulfonsäure mit einem Alkyloder Alkenylrest mit 12 bis 30 Kohlenstoffatomen. Unter den genannten Vertretern als Komponente b) sind die Metallseifen besonders bevorzugt.Preferred acids in the metal salt compound of the Component b) are also aliphatic or aromatic Sulfonic acids with 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms, in aliphatic or aromatic radical. The aliphatic The rest can be straight or branched, saturated or be unsaturated. The aromatic sulfonic acid is preferably a benzenesulfonic acid with an alkyl or Alkenyl radical with 12 to 30 carbon atoms. Under the representatives mentioned as component b) are Metal soaps are particularly preferred.

    Die erfindungsgemäß als Komponente b) einzusetzenden organischen Metallsalze können nach den im Stand der Technik beschriebenen Methoden hergestellt werden. Dabei sei insbesondere auf die eingangs genannten Druckschriften FR-A-2 172 797, FR-A-2 632 966, US-A-4 129 589 und EP-A-476 196 hingewiesen, die hier miteinbezogen werden. Die erfindungsgemäß einzusetzenden organischen Metallsalze sollen öllöslich oder zumindest öldispergierbar sein. Es handelt sich ferner um ein neutrales oder basisches Produkt, wobei letzteres bevorzugt ist. Der Ausdruck "basisch" bezeichnet bekanntlich solche Metallsalze, in denen das Metall in einer stöchiometrisch größeren Menge als das organische Säureradikal vorliegt. Die erfindungsgemäß einzusetzenden basischen Metallsalzprodukte weisen demnach einen pH-Wert von im allgemeinen 7,5 bis 12 auf, vorzugsweise von 8 bis 10.Those to be used according to the invention as component b) organic metal salts can according to the state of the art Techniques described methods can be produced. there be particularly to the above Documents FR-A-2 172 797, FR-A-2 632 966, US-A-4 129 589 and EP-A-476 196, which are here be included. The to be used according to the invention organic metal salts are said to be oil-soluble or at least be oil dispersible. It is also a neutral or basic product, the latter is preferred. The term "basic" denotes as is known such metal salts in which the metal in a stoichiometrically larger amount than the organic one Acid radical is present. The invention have basic metal salt products to be used accordingly a pH of generally 7.5 to 12, preferably from 8 to 10.

    Die-Herstellung des erfindungsgemäßen verwendeten Additivs erfolgt durch Zusammenmischen der Komponenten a) und b), gegebenenfalls unter Verwendung eines Lösungs- oder Dispergiermittels. Geeignete derartige Mittel sind niedere oder höhere Alkohole wie Ethanol, Isopropanol, Butanol, Decanol, Dodecanol und dergleichen, niedere oder höhere Glykole und deren Mono- oder Dialkylether wie Ethylenglykol, Propylenglykol, Diethylenglykol, Tetraethylenglykol, Tetrapropylenglykol und dergleichen, niedrig- bis mittelhochsiedende aliphatische, aromatische oder cycloaliphatische Kohlenwasserstoffe wie Toluol, Xylol, Naphtha und dergleichen, leichte bis mittelschwere Mineralöle, Öldestillate, natürliche oder synthetische Öle und Derivate davon sowie Mischungen von zwei oder mehreren dieser Lösungsmittel. Das Zusammenbringen der beiden Komponenten, Aminverbindung und Metallsalzverbindung, erfolgt im allgemeinen bei Atmosphärendruck und einer Temperatur von 15 bis 100 °C, vorzugsweise 20 bis 70 °C.The additive used according to the invention is produced by mixing components a) and b) together, optionally using a solution or Dispersant. Suitable such means are lower or higher alcohols such as ethanol, isopropanol, Butanol, decanol, dodecanol and the like, lower or higher glycols and their mono- or dialkyl ethers such as ethylene glycol, propylene glycol, diethylene glycol, Tetraethylene glycol, tetrapropylene glycol and the like, low to medium high boiling aliphatic, aromatic or cycloaliphatic hydrocarbons such as toluene, xylene, naphtha and the like, light to medium heavy mineral oils, oil distillates, natural or synthetic oils and derivatives thereof and mixtures of two or more of these solvents. The Bringing the two components together, amine compound and metal salt compound, generally takes place at Atmospheric pressure and a temperature of 15 to 100 ° C, preferably 20 to 70 ° C.

    Die schweren Öle sind gekennzeichnet durch einen Gehalt an dem beschriebenen Additiv. Die wirksame Menge an Additiv im schweren Öl kann in weiten Grenzen variieren. Im allgemeinen enthält das Öl 2 bis 2000 ppm Additiv, vorzugsweise 100 bis 1000 ppm.The heavy oils are marked by a content of the additive described. The effective amount of additive in heavy oil can vary widely Limits vary. Generally the oil contains 2 to 2000 ppm additive, preferably 100 to 1000 ppm.

    Das erfindungsgemäße Verwendeten Additiv und die Schweröle mit diesem Additiv weisen ein besonders erwünschtes Eigenschaftsbild auf, und dies dürfte vor allem auf einen unerwartet hohen Synergismus der erfindungsgemäßen Verwendeten Kombination der Komponenten a) und b) beruhen. So liegt das Additiv im Öl gelöst oder hochverteilt vor. Auch in Ölen mit einem hohen Gehalt an Asphaltenen und/oder anderen höher molekularen Verbindungen sind all diese unlöslichen Anteile gut emulgiert oder dispergiert. Das gleiche gilt auch im Falle von Schlämmen, so daß auch Schlammbildung weitgehend ausgeschaltet oder zumindest deutlich verringert ist. Das erfindungsgemäße verwendeten Additiv ist ferner ein hochwirksamer Verbrennungsverbesserer. Es gewährleistet die vollständige Verbrennung von schweren Ölen unter gleichzeitiger Verminderung der Rußbildung. Die erfindungsgemäßen Schweröle erfüllen also die eingangs genannten Forderungen in einem überraschend hohen Ausmaß. Infolge der genannten Wirkungen führt das erfindungsgemäße Additiv zu Ölen, die darüber hinaus insbesondere auch die folgenden vorteilhaften Eigenschaften aufweisen: verbesserte Lagerstabilität (verringerte Abscheidung unlöslicher Bestandteile), verbesserte Pumpbarkeit durch niedrige Viskosität, längere Standzeit der Filtersysteme, verbessertes Einspritzverhalten an den Verbrennungseinrichtungen, was zusätzlich zur Optimierung der Verbrennung beiträgt, und erhöhter Korrosionsschutz für alle Einrichtungen durch die gute Korrosionsinhibierung des Additivs. Die schweren Öle werden demnach vor allem als Brennstoff für Industrieanlagen und Kraftwerke verwendet und ebenso als Treibstoff für Schiffsmotoren.The additive used according to the invention and the heavy oils with this additive have a particularly desirable one Property profile on, and this should be mostly on an unexpectedly high synergism of those used according to the invention Combination of components a) and b) are based. So lies the additive dissolved or highly distributed in the oil. Also in Oils with a high content of asphaltenes and / or other higher molecular compounds are all of these insoluble parts well emulsified or dispersed. The the same applies in the case of sludge, so that too Sludge formation largely eliminated or at least is significantly reduced. The additive used according to the invention is also a highly effective combustion improver. It ensures the complete combustion of heavy Oil while reducing soot formation. The heavy oils according to the invention thus fulfill the requirements mentioned in a surprising high degree. As a result of the effects mentioned additive to oils according to the invention, moreover especially the following advantageous ones Features: improved storage stability (reduced separation of insoluble components), improved pumpability due to low viscosity, longer service life of the filter systems, improved Injection behavior at the combustion devices what additionally contributes to the optimization of the combustion, and increased corrosion protection for all facilities the good corrosion inhibition of the additive. The heavy oils are therefore, above all as fuel for industrial plants and power plants used and also as a fuel for marine engines.

    Die Erfindung wird nun an Beispielen und Vergleichsbeispielen noch näher erläutert.

    • Komponente a) des erfindungsgemäßen verwendeten Additivs:
      Als Komponente a) werden die Verbindungen a1, a3 und a5 von Tabelle 1 eingesetzt.
    • Komponente b) des erfindungsgemäßen verwendeten Additivs:
      Als Komponente b) werden die nachstehend näher beschriebenen Produkte b1 und b2 eingesetzt.
    The invention will now be explained in more detail using examples and comparative examples.
    • Component a) of the additive used according to the invention:
      Compounds a 1 , a 3 and a 5 from Table 1 are used as component a).
    • Component b) of the additive used according to the invention:
      Products b 1 and b 2 described in more detail below are used as component b).

    - Produkt b1:- Product b 1 :

    Die zur Herstellung von Produkt b1 verwendete Fettsäure ist eine destillierte Fettsäure, bestehend aus einer Mischung (Blend) von destillierter Talköl-Fettsäure und Harzsäure mit einem Molekulargewicht von etwa 300 g/mol. Ansatz: FeCl3 0,85 l Dichte 1,48 g/cm3 NH3 0,785 l Dichte 0,91 g/cm3 Fettsäure 0,22 l Dichte 0,94 g/cm3 Wasser 0,20 l Petroleum-Destillat 0,80 l Dichte 0,82 g/cm3 The fatty acid used to produce product b 1 is a distilled fatty acid consisting of a mixture (blend) of distilled talc oil fatty acid and resin acid with a molecular weight of about 300 g / mol. Approach: FeCl 3 0.85 l Density 1.48 g / cm 3 NH 3 0.785 l Density 0.91 g / cm 3 fatty acid 0.22 l Density 0.94 g / cm 3 water 0.20 l Petroleum distillate 0.80 l Density 0.82 g / cm 3

    Die 0,85 l FeCl3, 0,22 l Fettsäure, 0,20 l Wasser und 0,80 l Petroleum Destillat werden bei Raumtemperatur (15 bis 30 °C) miteinander vermischt. In diese Mischung werden unter Rühren die 0,785 l NH3 langsam eingebracht (exotherme Reaktion). Die Mischung wird unter Rühren auf 80 bis 90 °C erhitzt, wobei sich eine wäßrige und eine organische Phase bilden. Die Phasenbildung kann durch Zusatz von weiterem Petroleumdestillat vervollständigt werden. Die beiden Phasen werden voneinander getrennt (dekantiert), worauf die organische Phase zur Abtrennung von Restwasser noch zentrifugiert wird. Die organische Phase enthält die gewünschte Eisencarboxylat-Verbindung.The 0.85 l FeCl 3 , 0.22 l fatty acid, 0.20 l water and 0.80 l petroleum distillate are mixed together at room temperature (15 to 30 ° C). The 0.785 l of NH 3 are slowly introduced into this mixture with stirring (exothermic reaction). The mixture is heated to 80 to 90 ° C. with stirring, an aqueous and an organic phase being formed. The phase formation can be completed by adding more petroleum distillate. The two phases are separated from one another (decanted), whereupon the organic phase is still centrifuged to remove residual water. The organic phase contains the desired iron carboxylate compound.

    - Produkt b2:- Product b 2 :

    Die zur Herstellung von Produkt b2 verwendete Fettsäure ist eine Alkylbenzolsulfonsäure mit einem Molekulargewicht von etwa 322 g/mol. Ansatz: FeCl3 44 ml Dichte 1,48 g/cm3 NH3 34 ml Dichte 0,91 g/cm3 Säure 13 ml Dichte 1,06 g/cm3 Wasser 16 ml Petroleum-Destillat 84 ml Dichte 0,82 g/cm3 The fatty acid used to produce product b 2 is an alkylbenzenesulfonic acid with a molecular weight of approximately 322 g / mol. Approach: FeCl 3 44 ml Density 1.48 g / cm 3 NH 3 34 ml Density 0.91 g / cm 3 acid 13 ml Density 1.06 g / cm 3 water 16 ml Petroleum distillate 84 ml Density 0.82 g / cm 3

    Die Herstellung von Produkt b2, ein
    Eisenalkylbenzolsulfonat, erfolgt analog Produkt b1. Erfindungsgemäße verwendeten Additive:    The production of product b 2 , a
    Eisenalkylbenzenesulfonat, takes place analogously to product b 1 . Additives used according to the invention:

    Beispiel 1example 1

  • a) 40 Gew.-% von Verbindung a1 a) 40% by weight of compound a 1
  • b) 60 Gew.-% vom organischen Eisensalz gemäß Produkt b1 b) 60% by weight of the organic iron salt according to product b 1

    • Beispiel 2Example 2

  • a) 60 Gew.-% von Verbindung a3 a) 60% by weight of compound a 3
  • b) 40 Gew.-% vom organischen Eisensalz gemäß Produkt b2 b) 40% by weight of the organic iron salt according to product b 2

    • Beispiel 3Example 3

  • a) 50 Gew.-% von Verbindung a5 a) 50% by weight of compound a 5
  • b) 50 Gew.-% vom organischen Eisensalz gemäß Produkt b1 b) 50% by weight of the organic iron salt according to product b 1

    • Die erfindungsgemäßen verwendeten Additive der Beispiele 1 bis 3 werden durch Zusammenmischen der Komponenten a) und b) hergestellt (Mischtemperatur etwa 20 bis etwa 60 °C). Nach einer bevorzugten Arbeitsweise wird zunächst die Komponente a) vorgelegt und unter Rühren und Stickstoffatmosphäre auf etwa 40 bis 50 °C erhitzt. Nun wird bei der genannten Temperatur die Komponente b) unter Stickstoffatomsphäre eingerührt, worauf das erfindungsgemäße Additiv hergestellt ist. Sollte die auf Raumtemperatur abgekühlte Mischung die gewünschte Viskosität nicht aufweisen und/oder eine Phasentrennung zu beobachten sein, können diese Erscheinungen dadurch beseitigt werden, daß man der Mischung eine wirksame Menge von einem organischen Lösungsmittel wie Petroleumdestillat hinzufügt.

    • Test der erfindungsgemäßen verwendeten Additive:
      Die Additive der Beispiele 1 bis 3 werden bezüglich Asphalten-Dispergierbarkeit und Verbesserung der Verbrennbarkeit von Schwerölen getestet. Für den Test der Asphalten-Dispergierbarkeit wird zunächst eine Asphaltene enthaltende Lösung hergestellt.
    • Herstellung einer Lösung von Asphaltenen in Toluol:
      Zur Herstellung dieser Lösung wird ein Asphaltene enthaltendes Rückstandsöl einer Extraktion unterworfen, die im einzelnen wie folgt durchgeführt wird. In einem ersten Schritt werden etwa 30 g Rückstandsöl in einem Becherglas mit etwa 300 ml Essigsäureethylester versetzt. Die Mischung wird 2 Stunden bei 40 °C gerührt und danach 24 Stunden lang stehengelassen, worauf sie über ein einfaches Porenfilter abfiltriert wird. In einem zweiten Schritt wird der Filterrückstand in eine für Soxhlet-Extraktion übliche Extraktionshülse gegeben und mit Hilfe von wiederum etwa 300 ml Essigsäureethylester etwa 2 Stunden lang extrahiert, wobei der Paraffin-Anteil im Filterkuchen in die Essigsäureethylester-Phase übergeht. In einem dritten Schritt werden mit Hilfe von etwa 300 ml Pentan die Harzanteile ebenfalls durch Soxhlet-Extraktion herausgelöst. In einem vierten Schritt werden dann mit Hilfe von etwa 300 ml Toluol die Asphaltene extrahiert, wobei die gewünschte Lösung von Asphaltenen in Toluol erhalten wird.
    • Test der erfindungsgemäßen verwendeten Additive auf
      Asphalten-Dispergierbarkeit: Dieser Test wird nach den Vorschriften ISO 10307-1:1993 oder ASTM D4370-32 (Heißfiltration) durchgeführt. Dazu werden zunächst 30 g von einer etwa 10gew.%igen Asphalten-Lösung in Toluol mit 100 ml Pentan vermischt. In drei solche Asphalten-Toluol/Pentan-Lösungen werden jeweils 700 ppm Additiv vom Beispiel 1, 2 und 3 bei Raumtemperatur eingerührt. Diese drei Testlösungen werden dann gemäß den genannten Vorschriften behandelt. Ergebnis: Die erfindungsgemäßen verwendeten Additive erfüllen den Test.
    • Test der erfindungsgemäßen verwendeten Additive auf Verbesserung der Verbrennbarkeit von Schwerölen:
      Dieser Test wird nach den Vorschriften von VDI 2066, Blatt 1 (VDI heißt Verein deutscher Ingenieure) durchgeführt, wobei die Additive der Beispiele 1, 2 und 3 in einer Menge von 500 ppm, 700 ppm und 900 ppm eingesetzt werden. Ergebnis: Die erfindungsgemäßen verwendeten Additive erfüllen den Test.
    The additives used according to the invention from Examples 1 to 3 are prepared by mixing components a) and b) together (mixing temperature about 20 to about 60 ° C.). According to a preferred procedure, component a) is initially introduced and heated to about 40 to 50 ° C. with stirring and under a nitrogen atmosphere. At this temperature, component b) is then stirred in under a nitrogen atmosphere, after which the additive according to the invention is produced. If the mixture cooled to room temperature does not have the desired viscosity and / or a phase separation can be observed, these phenomena can be eliminated by adding an effective amount of an organic solvent such as petroleum distillate to the mixture.
    • Test of the additives used according to the invention:
      The additives of Examples 1 to 3 are tested for asphaltene dispersibility and to improve the combustibility of heavy oils. For the asphaltene dispersibility test, a solution containing asphaltenes is first prepared.
    • Preparation of a solution of asphaltenes in toluene:
      To prepare this solution, an asphaltene-containing residual oil is subjected to an extraction, which is carried out in detail as follows. In a first step, about 30 g of residual oil are mixed with about 300 ml of ethyl acetate in a beaker. The mixture is stirred at 40 ° C. for 2 hours and then left to stand for 24 hours, after which it is filtered off through a simple pore filter. In a second step, the filter residue is placed in an extraction sleeve customary for Soxhlet extraction and extracted with the aid of again about 300 ml of ethyl acetate for about 2 hours, the paraffin portion in the filter cake passing into the ethyl acetate phase. In a third step, the resin components are also extracted by Soxhlet extraction with the help of approximately 300 ml of pentane. In a fourth step, the asphaltenes are then extracted with the aid of about 300 ml of toluene, the desired solution of asphaltenes in toluene being obtained.
    • Test of the additives used according to the invention
      Asphaltene dispersibility: This test is carried out in accordance with ISO 10307-1: 1993 or ASTM D4370-32 (hot filtration). For this purpose, 30 g of an approximately 10% by weight asphaltene solution in toluene are first mixed with 100 ml of pentane. 700 ppm of additive from Examples 1, 2 and 3 are stirred into three such asphaltene-toluene / pentane solutions at room temperature. These three test solutions are then treated in accordance with the regulations mentioned. Result: The additives used according to the invention meet the test.
    • Test of the additives used according to the invention for improving the combustibility of heavy oils:
      This test is carried out according to the regulations of VDI 2066, Sheet 1 (VDI means Association of German Engineers), the additives of Examples 1, 2 and 3 being used in an amount of 500 ppm, 700 ppm and 900 ppm. Result: The additives used according to the invention meet the test.

    Vergleichsbeispiele 1 bis 3Comparative Examples 1 to 3

    In den Vergleichsbeispielen 1 bis 3 werden die Verbindungen a1, a3 und b1 jeweils allein eingesetzt. Die drei Testlösungen werden dem gleichen Prüfverfahren wie die erfindungsgemäßen Beispiele-unterzogen. Ergebnis: Alle Testlösungen erfüllen weder den Test auf Asphalten-Dispergierbarkeit noch jenen auf Verbesserung der Brennbarkeit.In Comparative Examples 1 to 3, the compounds a 1 , a 3 and b 1 are each used alone. The three test solutions are subjected to the same test procedure as the examples according to the invention. Result: All test solutions do not meet the asphaltene dispersibility test or the combustibility improvement test.

    Die erfindungsgemäßen verwendeten Additve besitzen also eine unerwartet hohe Wirksamkeit bezüglich Dispergierung von Asphaltenen in Schwerölen und auch bezüglich Verbrennung von Schwerölen; dies dürfte aus einem überraschend hohen Synergismus der Additiv-Komponenten a) und b) resultieren. Aufgrund der vorteilhaften Wirkungen des neuen Additivs weisen die Öle vor allem auch jene Eigenschaften auf, die für den Einsatz in Industrieanlagen, Kraftwerken und schweren Schiffsmotoren besonders gewünscht werden.The invention The additives used therefore have a unexpectedly high effectiveness regarding dispersion of Asphaltenes in heavy oils and also with regard to combustion of heavy oils; this should come from a surprisingly high Synergism of additive components a) and b) result. Because of the beneficial effects of The oils show new additives all those properties that are essential for use in industrial plants, power plants and heavy Ship engines are particularly desired.

    Claims (8)

    1. The use of an additive, essentially comprising
      a) 1 to 99% by weight, of at least one amine compound of the formula (I) below
      Figure 00210001
      in which
      n
      is 1, 2, 3 or 4,
      A
      is a radical of the formulae (II) to (V)
      Figure 00210002
      Figure 00210003
         where R is a C6 to C22 alkyl, and
      m
      is 2, 3 or 4,
      x
      is a number from 5 to 120,
      R1
      is H, CH3 or H and CH3, where the oxyalkylene radicals are arranged randomly or in blocks, and
      b) 1 to 99% by weight, of at least one oil-soluble or oil-dispersible neutral or basic metal salt compound containing a metal of the first main group of the Periodic Table of the Elements, of the second main group, of the first subgroup, of the second subgroup, of the fourth subgroup, of the sixth subgroup, of the eighth subgroup or of the lanthanide group of the Periodic Table of the Elements, and a carboxylic acid, sulfonic acid, acid ester of phosphoric acid or acid ester of sulfuric acid containing a hydrocarbon radical of in each case 8 to 40 carbon atoms as acid component, percentages by weight based on the additive, as emulsifier and dispersant and as a combustion enhancer for heavy oils.
    2. The use as claimed in claim 1, wherein the component a) is an amine compound of the formula (VI) below
      Figure 00220001
      in which
      n
      is 1, 2, 3 or 4,
      A
      is a radical of the specified formulae (II) to (V),
      a
      is a number from 5 to 30,
      b
      is a number from 5 to 50 and
      c
      is a number from 0 to 40.
    3. The use as claimed in claim 1 or 2, wherein the component b) is a metal salt compound containing a metal selected from the group consisting of alkali metals, alkaline earth metals, copper, silver, zinc, cadmium, titanium, zirconium, molybdenum, chromium, tungsten, iron, cobalt, nickel, lanthanum, cerium and ytterbium, and containing an acid selected from the group consisting of aliphatic carboxylic acids having 8 to 40 carbon atoms, dimeric fatty acids having 36 carbon atoms and aliphatic or aromatic sulfonic acids having 8 to 40 carbon atoms.
    4. The use as claimed in claim 1 or 2, wherein the component b) is a metal salt compound, the metal being an alkaline earth metal, copper, zinc, zirconium, molybdenum, iron, nickel, cerium or ytterbium, and the acid component being a fatty acid having 8 to 40 carbon atoms, a dimeric fatty acid having 36 carbon atoms or an aliphatic or aromatic sulfonic acid having 8 to 40 carbon atoms.
    5. The use as claimed in one or more of claims 1 to 4, wherein it contains 20 to 80% by weight of the component a) and 20 to 80% by weight of the component b).
    6. The use as claimed in one or more of claims 1 to 4, wherein it contains 40 to 60% by weight of component a) and 40 to 60% by weight of component b).
    7. The use as claimed in one or more of claims 1 to 6, wherein it has a pH of 7.5 to 12.
    8. The use of the additive as claimed in one or more of claims 1 to 7 in industrial plants, power stations or marine engines.
    EP97912206A 1996-10-30 1997-10-21 Utilisation d'un additif pour ameliorer les proprietes d'huiles lourdes Expired - Lifetime EP0938534B1 (en)

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    DE19643832A DE19643832A1 (en) 1996-10-30 1996-10-30 Heavy oils with improved properties and an additive for them
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    US6488724B1 (en) 2002-12-03
    AU4948797A (en) 1998-05-22
    CA2270218A1 (en) 1998-05-07
    HUP9904230A3 (en) 2001-02-28
    HUP9904230A2 (en) 2000-04-28
    DE59704734D1 (en) 2001-10-31
    DK0938534T3 (en) 2001-12-17
    DE19643832A1 (en) 1998-05-07
    RU2177980C2 (en) 2002-01-10
    MY121236A (en) 2006-01-28
    ZA979704B (en) 1998-07-27
    CA2270218C (en) 2006-10-31
    NO991949D0 (en) 1999-04-23
    BR9712463A (en) 1999-12-21
    EP0938534A1 (en) 1999-09-01
    WO1998018885A1 (en) 1998-05-07
    AR008902A1 (en) 2000-02-23
    ES2165031T3 (en) 2002-03-01
    TR199900929T2 (en) 1999-07-21
    UA52704C2 (en) 2003-01-15
    CN1235629A (en) 1999-11-17
    NO991949L (en) 1999-04-23
    AU727164B2 (en) 2000-12-07
    CO4870788A1 (en) 1999-12-27

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